Coating, ink, or article comprising multi-colored lustrous pearlescent pigments

ABSTRACT

A coating, ink, or article containing a pearlescent pigment comprising a substrate and a first layer, wherein the first layer comprises iron oxide, wherein the iron has from about 1% to about 30% Fe(II) and from about 70% to about 99% Fe(III).

CROSS REFERENCE TO RELATED APPLICATIONS

The present application hereby claims the benefit of the non-provisional patent application Ser. No. 11/765,614, filed on Jun. 20, 2007, and the provisional patent application Ser. No. 60/865,042, filed on Nov. 9, 2006, the disclosures of which are hereby incorporated by reference in their entirety.

BACKGROUND OF THE INVENTION

The present invention relates, in general, to multi-colored lustrous pearlescent pigments.

Along with gem stones (e.g., diamond, ruby, emerald, topaz, opal, jade), and precious metals (e.g., gold, silver, platinum), pearls are among the most prized possessions (or luxury items) for human beings for millenniums. Beside their natural beauty, the brilliant color and luster, they are often associated with social status and level of well-being. As a result, and not surprisingly, the trend of cosmetics makeup is to emulate or recreate these “natural” and “aesthetic” appearances of pearl, gem and precious metals with less expensive materials such as interference pigments (e.g., metal oxide coated mica). The most common types of pearlescent pigments are micronized titanium dioxide, metal oxide coated mica, metal oxide coated alumina, metal oxide coated silica, basic lead carbonate, bismuth oxychloride, and natural fish silver.

Metal oxide coated mica pigments are characterized by excellent optical, chemical, mechanical, toxicological, and environmental properties. Natural or synthetic mica, and alternative supports, such as aluminum flakes, or SiO₂ platelets, can be used alone, or as a support for titanium dioxide, iron oxide (Fe₂O₃ or Fe₃O₄), iron ferrocyanide (Iron Blue or Prussian Blue), tin oxide, and chromium oxide. The color space defined by these coated mica-based pigments is based on the type of coating (e.g. metal oxide, colorant, etc.) used, the layer thickness, and the number of coated layers.

Among the natural pearls, the most expensive are black pearls, which come with various undertone and color flops. To faithfully emulate this aesthetic optical effect in cosmetic makeup is one of the top challenges facing a cosmetic pigment maker and formulator. The traditional approach to these pigments is to blend dark solid-color inorganic pigment (e.g., carbon black) with white platy pearlescent pigments (e.g., TiO₂ coated mica, TiO₂ coated borosilicate, TiO₂ coated alumina). The platy interference pigment provides the luster, brilliance (reflection), transparency and depth of field. The solid-color pigment(s) provide(s) the dark undertone and surface coverage. However, this type of blend usually appears to be much “dirtier”, “lack luster”, and “lack transparency” compared to the natural pearl. The primary reason for that is fouling of the smooth surface of white pearlescent pigment by the solid-color pigment granules, which leads to light scattering and disruption of light interference.

Metal oxide coated platelet pigments may be magnetic or exhibit magnetic susceptibility. When placed into a liquid coating, regions of the coated pigment may be aligned by an externally applied magnetic field and produce a goniochromatic, or angle dependent optical effect. This effect may be used to create an impression of a two- or three-dimensional image. After the pigments have been aligned, the coating may be cured to solidify the optical effect. Examples of pigments and methods of aligning them are discussed in U.S. Pat. No. 6,589,331, U.S. Pat. No. 6,902,807, U.S. Pat. No. 5,223,360, U.S. Pat. No. 6,759,097, and U.S. Pat. No. 7,258,900. However, the magnetic pigments are significantly limited in terms of color space. The typical colors available are metallic black, grey shades, or bichromic shades characterized by a black or reddish brown absorbance color combined with a weak interference color.

A need exists to expand the existing color space of metal oxide coated pigments to more vibrant, lustrous colored shades, as well as, antique dark pearlescent shades, using a processing method that allows for optimal control of color and opacity. In addition, a need exists for more colorful magnetic pigments that have a larger color contrast between aligned and non-aligned pigments.

BRIEF SUMMARY OF THE INVENTION

The invention overcomes the above-noted and other deficiencies of the prior art by providing a pearlescent pigment comprising a substrate and a first layer, wherein the first layer comprises iron oxide, wherein the iron in the iron oxide comprises from about 10% to about 20% Fe(II), and from about 80% to about 90% Fe(III).

Another aspect of the invention is a pearlescent pigment, wherein the pigment is an inorganic material and the color of a homogeneous coating of the pigment, measured over a white background, is selected from the group consisting of: a CIELAB hue angle, h_(ab), from about 50 to about 80 degrees, wherein L* is not more than about 85, and the chroma value is greater than 22; a CIELAB hue angle, h_(ab), from about 80 to about 275 degrees, wherein L* is not more than about 80, and the chroma value is greater than about 10; and a CIELAB hue angle, h_(ab), from not less than about 275 to not more than about 50 degrees, wherein L* is not more than about 85, and the chroma value is greater than about 9.

Another aspect of the invention is a pearlescent pigment, wherein the pearlescent pigment is an inorganic material and the color of a homogeneous coating of the pigment, measured over a white background, has a CIELAB L* value of about 30 or less and a chroma value of about 3 or less.

Another aspect of the invention is a pearlescent pigment, wherein the pigment is prepared by coating a substrate with a metal oxide to form a first layer, and reducing the metal oxide of the first layer, wherein only about 10% to about 20% of the metal is reduced.

Another aspect of the invention is a pearlescent pigment, wherein the homogeneous pearlescent pigment is an inorganic material and the ΔE* between the magnetically aligned and non aligned pigment as measured over a white background is not less than 20.

Another aspect of the invention is a process for reducing a metal oxide coated substrate with a hydrogen source in the presence of a noble metal catalyst.

Another aspect of the invention is a process for making a pearlescent pigment, comprising reducing an iron oxide coated substrate with a hydrogen source, wherein only about 1% to about 30% of the iron is reduced.

Another aspect of the invention is a highly active catalyst, comprising a nanoparticulate noble metal in a polyvinylpyrrolidone (PVP) polymer, or other polymer.

Another aspect of the invention is a cosmetic formulation containing a pearlescent pigment comprising a substrate and a first layer, wherein the first layer comprises iron oxide, wherein the iron in the iron oxide comprises from about 10% to about 20% Fe(II), and from about 80% to about 90% Fe(III).

Another aspect of the invention is a cosmetic composition containing a pearlescent pigment comprising a substrate and a first layer, wherein the first layer contains iron oxide, wherein the iron of the iron oxide has from about 1% to about 30% Fe(II) and from about 70% to about 99% Fe(III).

Another aspect of the invention is a paint or ink composition containing a pearlescent pigment comprising a substrate and a first layer, wherein the first layer comprises iron oxide, wherein the iron of the iron oxide has from about 1% to about 30% Fe(II) and from about 70% to about 99% Fe(III).

Another aspect of the invention is a plastic composition containing a pearlescent pigment comprising a substrate and a first layer, wherein the first layer comprises iron oxide, wherein the iron of the iron oxide has from about 1% to about 30% Fe(II) and from about 70% to about 99% Fe(III).

These and other objects and advantages of the present invention shall be made apparent from the accompanying drawings and the description thereof.

BRIEF DESCRIPTION OF THE FIGURES

FIG. 1 is a graph of the CIELAB a* and b* color coordinates of Examples 14-16 as measured against a black background.

FIG. 2 is the visible spectra of the filtrates of the pigments tested in Example 18

DETAILED DESCRIPTION OF THE INVENTION

The present invention relates to lustrous, pearlescent pigments with controlled opacity, comprising a substrate and a first layer, wherein the first layer comprises iron oxide, wherein the iron in the iron oxide comprises from about 1% to about 30% Fe(II) and from about 70% to about 99% Fe(III).

Iron oxide coated substrates exhibit intensely colored pearlescent pigments with high luster. Varying the substrate, the iron oxide layer thickness, and the amount of Fe(II) and Fe(III) in the layer will change the color, luminosity, and transparency of the pigment. The mean thickness of the first layer may be from about 1 nm to about 350 nm, from about 10 nm to about 350 nm, or from about 10 nm to about 250 nm.

In one embodiment, the pigment may comprise a second layer located between the substrate and the first layer, wherein the second layer has a refractive index of greater than about 1.6 or less than about 1.4. The second layer may have a refractive index equal to or greater than about 1.8. Examples of compounds that may be used as the second layer are: TiO₂, Fe₂O₃, ZrO₂, SnO₂, Cr₂O₃, BiOCl, and ZnO. The second layer may comprise one or more materials. The second layer may be TiO₂. The second layer may be an iron oxide, such as Fe₂O₃, Fe₃O₄, FeOOH, FeO, and Fe(OH)₃. The mean thickness of the second layer may be from about 50 nm to about 800 nm, or from about 100 nm to about 600 nm.

In another embodiment, titanium oxide coated mica pigments exhibit pearlescent effects resulting from reflection and light interference. The interference color and luster is dependent on the thickness of the TiO₂ surface layer and its corresponding surface roughness. This initial interference color of the pigment, prior to the coating of the first layer is apparent when viewed against a black background. It has been surprisingly discovered that FeOOH deposition followed by reduction results in the advancement of the interference color and a significant increase in opacity of TiO₂ coated platelet-like pigments. This process transforms the transparent, TiO₂ coated mica, into a lustrous colored pearlescent pigment with increased opacity. The thickness of the deposited FeOOH layer controls the magnitude of the color progression and opacity. For relatively thick FeOOH layers, the interference color progresses to the next shade and the pigment approaches complete opacity.

In order to improve the light, water repellency, weather stability, texture, and dispersion ability, it is frequently advisable to subject the finished pigment to surface treatment, depending on the area of application. Examples of surface treatments are methicone (poly(oxy(methylsilylene))), metal soap, fatty acid, hydrogenated lecithin, dimethicone (polydimethylsiloxane), fluorinated compounds, amino acids, N-acylamino acids, glyceryl rosinates, silanes, and combinations. Many of the processes are described in U.S. Pat. No. 6,790,452; U.S. Pat. No. 5,368,639; U.S. Pat. No. 5,326,392; U.S. Pat. No. 5,486,631; U.S. Pat. No. 4,606,914; U.S. Pat. No. 4,622,074; German Patent 22 15 191; DE-A 31 51 354; DE-A 32 35 017; DE-A 33 34 598; DE 40 30 727 A1; EP 0 649 886 A2; WO 97/29059; WO 99/57204; U.S. Pat. No. 5,759,255; EP 0090259; EP 0 634 459; WO 99/57204; WO 96/32446; WO 99/57204; U.S. Pat. No. 5,759,255; U.S. Pat. No. 5,571,851; WO 01/92425; U.S. Pat. No. 5,472,491; J. J. Ponjee, Philips Technical Review, Vol. 44, No. 3, 81 ff; and P. H. Harding J. C. Berg, J. Adhesion Sci. Technol. Vol. 11 No. 4, pp. 471-493. This post-coating may further increase the chemical stability or simplify handling of the pigment, in particular incorporation into various media. In order to improve the wettability, dispersibility and/or compatibility with the user media, functional coatings of Al₂O₃ or ZrO₂ or mixtures thereof may be applied to the pigment surface.

In one embodiment, coupling agents may be used to form an outer layer on the pearlescent pigment. Suitable coupling agents are disclosed in EP 632 109. Examples include, silanes, zirconium aluminates, zirconates, and titanates. The silanes may possess the structure Y—(CH₂)_(n)—SiX₃ in which n is 2-8, Y is an organofunctional group, e.g. an amino, methacrylic, vinyl, alkyl, aryl, halogen and/or epoxy group, and X is a silicon-functional group which following its hydrolysis reacts with active sites of an inorganic substrate or by condensation with other silicon compounds. This group Y may comprise, for example a hydroxy, a halogen or an alkoxy group.

In addition to these substantially hydrophilic coupling agents, it is also possible to use hydrophilic silanes, especially the aryl-, alkyl- and fluoroalkyl-substituted di- and trimethoxysilanes. These include, for example, phenethyltrimethoxysilane, propyltrimethoxysilane, butyltrimethoxysilane, isobutyltrimethoxysilane, hexyltrimethoxysilane, octyltrimethoxysilane, 1H, 1H, 2H, 2H-perfluorodecyltrimethoxysilane and (3,3,3-trifluoropropyl)methyldimethoxysilane. The concentration of coupling agents may be 0.2-1.2% by weight with respect to the base pigment.

In one embodiment, the substrate is platelet-like and may have a mean thickness of about 0.05 to about 1.5 μm and a mean width of about 1 to about 750 μm. The substrate may have a mean width of about 10 to about 60 μm, about 5 to about 25 μm, about 10 to about 100 μm, about 40 to about 250 μm, or about 95 to about 730 μm.

As an example, when a relatively thin FeOOH coating on an iridescent blue TiO₂ coated laminar substrate (such as SunPearl Iridescent Blue by SunChemical) is reduced by hydrogenation, a semi-opaque lustrous blue-green or turquoise pearlescent pigment results (see Example 26). However, using this same iridescent blue substrate a thicker FeOOH coating will result in a lustrous green or olive pearlescent shade with increased opacity when reduced using similar hydrogenation conditions (see Example 27). This color advancement trend is applicable to many shades of TiO₂ coated laminar substrates. Therefore, more opaque blue pearlescent shades may be produced by reduction of iridescent violet TiO₂ coated substrates (such as SunPearl Iridescent Violet by SunChemical) containing thick FeOOH coatings (see Example 23). Likewise, less opaque green shades may be produced by reduction of iridescent green TiO₂ coated substrates (such as SunPearl Iridescent Green by SunChemical) having relatively thin FeOOH surface layers (see Example 8).

The synthesis of a particular colored pearlescent pigment begins with selection of the proper substrate material. The substrate may be comprised of natural mica, synthetic mica, glass flakes, Al₂O₃ platelets, SiO₂ platelets, BiOCl, borosilicate, synthetic alumina, and boron nitride. Such substrates may be multilayer materials, i.e. include materials of different refractive indices. The substrate may comprise mica. The pearlescent pigment may comprise a mixture of different substrates. Furthermore, the substrate may be made of identical or different flakes which differ in particle size.

The first step in forming a colored pearlescent pigment is to coat the substrate, or metal oxide coated substrate with a layer of non-annealed FeOOH, which is usually pale yellow in color. For the reasons of decreased crystallinity and higher surface area (porous microstructure), non-annealed FeOOH may be reduced to an iron oxide (FeO, FeO—Fe₂O₃, Fe₃O₄) under more mild reaction conditions, as compared to the more crystalline Fe₂O₃. The methods of deposition (or precipitation) of FeOOH or Fe(OH)₃ onto substrates are well known in the literature, for example as shown in Dyes and Pigments, 58 (2003), 239-244, U.S. Pat. No. 3,926,659, and in many scientific papers and patents particularly by Merck, Engelhard, and BASF. It is possible to start from a pre-coated substrate and coat this substrate with a metal oxide. Alternatively, the process may start from the substrate itself and a single coating may be used to reach the correct amount of iron oxide. Metal oxides other than FeOOH may used to the coat the substrate, or metal oxide coated substrate.

The basic principle of deposition is as follows: Fe³⁺ precursors such as ferric chloride, ferric sulfate, or both, are dissolved in an acidic medium containing the substrate. As the pH is increased by the addition of bases such KOH, NaOH, LiOH, and ammonia; Fe³⁺ ions are precipitated out as either colloidal FeOOH particles, or dense aggregates depending on the pH control profile, temperature and concentration, and in some case the presence of electrical field. In the presence of substrates with affinity to FeOOH, the colloidal particles can quickly form a uniform film on the substrate. The bonding between the deposited layer and substrate is usually a combination of metal oxide covalent bonds and hydrogen bonds. For example, in the case of making an antique burgundy pearlescent pigment, the substrate is hematite (red calcined Fe₂O₃) coated mica, which has extremely good affinity to FeOOH.

The traditional precipitation process utilizing KOH and NaOH is called a heterogeneous hydrolysis process. However, more recently, a newer process called homogenous hydrolysis, utilizes urea as an in situ generated base. This process is said to produce a smoother and more transparent metal oxide film as shown in Dyes and Pigments 58 (2003) 239-244, and Materials Research Bulletin (1999), vol. 34, no. 6, 905-914. The use of ferric sulfate may produce coarser particles, and weaker luster than ferric chloride. A computer-programmed rate-control heater may be used to better control the decomposition rate of urea, which in turn controls the rate of ammonia (base) generation. When the base generation rate is zero order (i.e., constant), the FeOOH colloids will nucleate and grow at a constant rate, and precipitate onto the substrate at a constant rate as well. As a result, a highly uniform film can be generated. At 80° C.-90° C., the urea hydrolysis is nearly zero order. This temperature range may be useful as the plateau (holding) temperature of the process. The amount of urea used is just enough to bring the final hydrolyzed solution pH to be between 6 and 8, in order to minimize the amount of free Fe³⁺ precursor left in the solution. Fe³⁺ is known to be at its lowest solubility around pH 8.

Depositing FeOOH by the Fe(III)-urea homogeneous hydrolysis may lead to uniform layers of FeOOH on the surface of the titanium dioxide coated mica substrates, which results in neon shaded pearlescent pigments (neon green-gold, neon pink, neon silver gold, etc.) that are not currently available commercially.

After deposition of a thin layer of FeOOH onto the colored substrate, the pigments are recovered from the solution by filtration. The pigments are washed multiple times with deionized water to remove residual urea, followed by drying to remove residual moisture. Following sufficient drying, the dry pigments are ready for reduction. Hydrogenation may be used to reduce the FeOOH layer. The resultant iron oxide (FeO, FeO—Fe₂O₃, Fe₃O₄) layer is typically darker in color, depending on the degree of reduction, thickness of the layer, and any other layers. Generally speaking, the more aggressive the hydrogenation conditions or the thicker the layer, the darker the final pigment will be. However, an overly thick iron oxide (FeO, FeO—Fe₂O₃, Fe₃O₄) layer will lead to some loss of transparency and luster. The reduction is performed so that the iron of the iron oxide typically comprises from about 1% to about 30% Fe(II) and from about 70% to about 99% Fe(III). The reduction may be performed so that the iron of the iron oxide comprises from about 12% to about 18% Fe(II) and from about 82% to about 88% Fe(III). The reduction may be performed so that the iron of the iron oxide comprises from about 14% to about 16% Fe(II) and from about 84% to about 86% Fe(III). In one embodiment, the amount of iron, in the iron oxide, is about 1% to about 15% of the weight of the pearlescent pigment.

Other metal oxides maybe reduced by this procedure. The reduction may be performed so that about 1% to about 30% of the metal in the metal oxide has been reduced. The reduction may be performed so that about 12% to about 18% of the metal in the metal oxide has been reduced. The reduction may be performed so that about 14% to about 16% of the metal in the metal oxide has been reduced. In one embodiment, the amount of metal, in the metal oxide, is about 1% to about 15% of the weight of the pearlescent pigment.

Homogeneous hydrogenation of suspensions containing metal oxide coated mica-based pigments allows much greater control of the oxidation state of the deposited iron oxide layers, compared to conventional high temperature calcination in a reducing (H₂/N₂) atmosphere. Thus, this processing technique may allow more precise control over pigment color and luster. In addition, the two step process of metal oxide deposition followed by liquid phase hydrogenation may yield pearlescent pigments with a smooth texture and improved rub-resistance relative to existing methodologies (e.g. mixtures, etc.). An example of the metal oxide that may be reduced is FeOOH.

One method of reduction uses a liquid-phase hydrogenation set-up consisting of three main components: 1) the hydrogen reservoir (equipped with N₂ purging); 2) a pressurized reaction chamber (with a 45° pitch agitation blade and an electrical heating mantle); and 3) a blow-out collector reservoir in case of over-pressure situation. The system is fully enclosed to minimize the risk of gas explosion. The pigments are first dispersed in a non-oxidizing (or mildly reductive) liquid, which has a reasonable H₂ gas solubility. Generally speaking, the higher the gas pressure, the higher the H₂ concentration in the carrying medium, and therefore the faster the reduction reaction. Higher temperatures and the addition of a noble metal catalyst also speed up the reaction. The degree of reduction, or the lightness (or darkness) of the final pigment are most effectively controlled by the length of reduction time and catalyst loading.

Some examples of solvents are PEG 400 (polyethylene glycol of molecular weight 425 g/mol) and NMP (N-methylpyrrolidone). Other solvents or liquids such as ethylene glycol, PEG 200, dimethylformamide and water can also be used. PEG 400 is most favored due to its high chemical stability (i.e., reusable for many runs), high boiling point (i.e., enabling high temperature reduction), low vapor pressure, low flammability, high H₂ solubility, good wetting power to the pigment (i.e., excellent dispersion and maximum surface exposure to H₂), good wetting power to the catalyst (i.e., maximize catalytic surface), and moderate viscosity (45 cP) for the ease of processing, which should be high enough to keep mica pigments from settling even under gentle agitation, and low enough to be filtered out under mild vacuum filtration condition. NMP may also be used. The hydrogenation pressure may be from atmospheric pressure, or above atmospheric pressure to about 70 bar. The pressure may be from about 10 bar to about 40 bar, or from about 10 to about 25 bar. The temperature may be from room temperature to about 220° C., or from 200-220° C., below the degradation temperature of the solvents. The agitation is usually kept below about 300 RPM to avoid fragmenting the pigment. The mica based pigments are usually very fragile and can break under high shear. Fragmentation usually leads to the rise of opacity and loss of luster. The concentration of the catalyst may be about 0.001 to about 0.2 g of catalyst per kilogram of liquid medium. In one embodiment the concentration of the catalyst may be about 0.01 to about 0.08 g of catalyst per kilogram of liquid medium.

Examples of noble metal catalysts include, but are not limited to Pd, Pt, PtO₂ (Adam's catalyst), Rh, Au, Ag, and Ta. The catalyst may be oxides, hydroxides or other derivatives of noble metals. The catalyst can come in supported or unsupported forms. Examples of supported forms include, but are not limited to Pd and Pt metals deposited onto charcoal or carbon based supports (coconut shell, etc.), alumina, zeolite or other inorganic substrates (support). The size of support can range from several millimeters to as small as 10-20 microns. Due to the higher surface to volume ratio, catalysts on smaller support can have a higher metal loading and thus higher catalytic activity. However, due to the size and density similarity to interference pigments, (i.e., 25-75 micron, SG of 3-5), catalysts of small support can be difficult to separate from the pigment, recover and reuse. The use of supported catalysts the size of about 1 mm and above, can be easily separated from pearlescent pigments by dry sieving using sieves of 80-120 mesh size. The large-support catalysts, including but not limited to Escat® 3 mm (Pt on alumina) are easily separated; they have relative low efficiency, and thus are useful for shallower hydrogenation that produces lighter color antique pearls such as antique copper and antique bronze.

Nanoparticulate metal catalysts are useful for deep hydrogenation to obtain extremely dark color. In one embodiment, commercially obtained bulk PtO₂ powder (usually 10-50 micron diameter) is wet milled with PEG400 in an intensive media mill using 0.5 mm zirconia media for 8 to 16 hours. The final particle size is submicron (i.e., colloidal size), and the PtO₂ can suspend in PEG 400 liquid for a couple days without settling. Since the majority of the interference pigment will settle in PEG 400 within an hour or so, sedimentation may be used as a separation process to recover colloidal PtO₂ from the pigment slurry. The majority of colloidal PtO₂ will remain in supernatant phase to be decanted and reused. Such method provides for an efficient liquid-phase hydrogenation of metal oxide coated mica pigments.

In one embodiment the catalyst nanoparticulate has a mean diameter from about 53 to about 55 nm. The median particle size may be about 40 nm.

A colloidal fluid of stabilized metal nanoparticles, such as Pt nanoparticles (Pt—NP) may be used as the catalyst for hydrogenation. Pt—NP catalytic fluid is prepared by a polymer stabilized direct-reduction method. The Pt nanoparticles are of 2-5 nm in size, and are stabilized by polyvinylpyrrolidone (PVP) polymer. This embodiment offers several benefits over micronized PtO₂ catalyst and industrially available hydrogenation catalysts mentioned above. First, it is thought that the extremely large surface area of Pt colloid allows for the use of less catalyst, and much more intimate contact between the catalyst and the substrate. Secondly, a small particle size and the presence of a lubricating polymer (PVP), help reduce the friction between the substrate and catalyst, which may lead to better preservation of surface smoothness and luster of the pigment. Third, this catalytic fluid is thermodynamically stable. The long shelf-life is a big advantage over the micronized PtO₂ catalyst, which requires periodically re-milling to sustain catalytic efficiency.

After hydrogenation, the pigment is subjected to an optional washing step to remove the Pt residue. PVP, a known chelating agent to Pt and a reducing agent to platinum salt, is useful as a 10% PVP aqueous washing solution to remove the free Pt—NP in the supernatant, Pt—NP absorbed onto substrate and any trace of Pt ions that might be present.

The deposition of FeOOH followed by hydrogenation may be utilized to progress the interference color associated with pearlescent, TiO₂ coated, mica-based pigments. Transparent, pearlescent TiO₂ coated pigments may be transformed into lustrous colored pearlescent pigments using the described methodology. For relatively thin FeOOH deposition, hydrogenation results in pigments characterized by the same interference color with increased opacity. The interference color may be progressed to the next shade (for instance, from violet to blue or blue to green) through reduction of relatively thick FeOOH coatings. This process also significantly increases the opacity of the resulting pearlescent pigment. Thus, various vibrant, multi-colored pigments may be produced in all four quadrants of the CIELAB color space with controlled opacity allowing for significantly improved formulation flexibility.

In one embodiment of a black/antique pearlescent pigment, the synthesis starts with choosing an appropriate substrate. The choice of substrate affects the undertone and transparency of color of the black/antique pearl interference pigment. For example, to yield an antique burgundy look, it is important to choose a substrate with deep red or deep maroon color, such as hematite (i.e., high temperature calcined Fe₂O₃) coated mica. This undertone in combination with an iron oxide (FeO, FeO—Fe₂O₃, Fe₃O₄) top layer will produce various shades of burgundy colors. Fe₂O₃ or TiO₂ coated synthetic or natural mica has colors ranging from red to yellow and blue to green. The color of substrate dictates the undertone of final pearl appearance. It is also desirable to choose a substrate with high transparency so that it can faithfully emulate the “airy” look of high quality natural pearl. Generally speaking synthetic mica (such those made by CQV), glass flakes layer (for instance from Nippon Sheet glass), borosilicate and synthetic alumina substrates are preferred over natural mica for higher transparency. Such substrates may be multilayer materials i.e. include materials of different refractive indices.

In one embodiment the pearlescent pigment is an inorganic material, and the color of a homogeneous coating of the pigment, measured over a white background, is selected from the group consisting of: a CIELAB hue angle, h_(ab), from about 50 to about 80 degrees, wherein L* is not more than about 85, and the chroma value is greater than 22; a CIELAB hue angle, h_(ab), from about 80 to about 275 degrees, wherein L* is not more than about 80, and the chroma value is greater than about 10; and a CIELAB hue angle, h_(ab), from not less than about 275 to not more than about 50 degrees, wherein L* is not more than about 85, and the chroma value is greater than about 9.

In one embodiment the pearlescent pigment is an inorganic material, and the color of a homogeneous coating of the pigment, measured over a white background has a CIELAB hue angle, h_(ab), from about 50 to about 80 degrees, wherein L* is not more than about 85, and the chroma value is greater than 22. The L* may be not more than about 80, about 75, or about 70. The chroma value may be greater than about 24, about 26, or about 28. In one embodiment the CIELAB hue angle, h_(ab), is from about 50 to about 65 degrees.

In one embodiment the pearlescent pigment is an inorganic material, and the color of a homogeneous coating of the pigment, measured over a white background has a CIELAB hue angle, h_(ab), from about 80 to about 275 degrees, wherein L* is not more than about 80, and the chroma value is greater than about 10. The L* may be not more than about 75, about 70, or about 65. The chroma value may be greater than about 12, about 14, or about 16.

In one embodiment the pearlescent pigment is an inorganic material, and the color of a homogeneous coating of the pigment, measured over a white background has a CIELAB hue angle, h_(ab), from not less than about 275 to not more than about 50 degrees, wherein L* is not more than about 85, and the chroma value is greater than about 9. The L* may be not more than about 80, about 75, or about 70. The chroma value may be greater than about 11, about 13, or about 15.

In one embodiment the pearlescent pigment is blue, with a CIELAB hue angle, h_(ab), from about 170 to about 275 degrees, measured over a white background using a D65 illuminant and a 10 degree observer. Blue pearlescent pigments may be produced that do not contain iron blue (ferric ferrocyanide), allowing the pigment to be used in cosmetic applications involving the lip area, such as lip gloss, lipstick, and other lip formulations. In addition, the blue pearlescent pigments are more stable than ferric ferrocyanide, which decomposes in alkaline pH resulting in pigment bleeding and marked changes in pigment color. Another advantage of the blue pearlescent pigments is that they do not restrict the pigment to the color space defined by ferric ferrocyanide. Iron Blue is a powerful colorant that only allows the pigment designer to formulate pigments within a well defined, narrow color space and restricts formulation flexibility, see Dyes and Pigments 56 (2003) 93-98.

In one embodiment the pearlescent pigment is green, with a CIELAB hue angle, h_(ab), from about 80 to about 170 degrees, measured over a white background using a D65 illuminant and a 10 degree observer. Green pearlescent pigments may be produced that do not contain chromium oxide, allowing the pigment to be used in cosmetic applications involving the lip area, such as lip gloss, lipstick, and other lip formulations. Most commercially available green pearlescent pigments are based on chromium oxide deposition, U.S. Pat. No. 6,485,556.

In one embodiment the pearlescent pigment is red, pink, or violet, with a CIELAB hue angle, h_(ab), from not less than about 275 to not more than about 50 degrees, measured over a white background using a D65 illuminant and a 10 degree observer. Red, pink, or violet mica-based pearlescent pigments may be produced that do not contain carmine. Carmine is a colorant used extensively in the cosmetic industry either directly or combined with pearlescent pigments (such as in Cloisonné® Red by Engelhard/BASF). It is extremely sensitive to UV exposure and may fade over time. Carmine is also unstable in acidic environments. It is often characterized by colorant bleeding in cosmetic formulations, such as nail polish. In addition, carmine (which is extracted from insects) has been linked to numerous reports of allergic reactions, including anaphylaxis. The development of carmine-free red, pink and violet shades is particularly advantageous because it offers formulators a more stable and hygienic alternative. In one embodiment the pearlescent pigment does not contain carmine.

In another embodiment, the pearlescent pigment has a HPI of less than about 1 when measured in a 76 μm thick film formed from 10 wt % of the pigment in acrylic enamel. The HPI may be less than about 0.5. The HPI may range from about 0.05 to about 0.5.

There are relatively few dark colored (or antique-looking) pearlescent pigments currently offered in the market, examples of such are: Timica® and Cloisonné Nu-Antique® lines by Engelhard/BASF. The existing dark pearlescent products in the market are too opaque and too dull (i.e., not enough luster), and not dark enough to emulate the natural black pearl effect (e.g., Tahiti black pearl). In addition, they exhibit an undesirable darkening effect when applied and rubbed on the skin. One method to solve these problems is to use a dark colored layer on top or beneath the interference layer as a smooth film, to minimize light scattering, and thus preserve the luster and transparency of the pigment.

In one embodiment the pearlescent pigment is an inorganic material and the color of a homogeneous coating of the pigment, measured over a white background, has a CIELAB L* value of about 30 or less and a chroma value of about 3 or less. The L* may be not more than about 28, about 25, or about 22. The chroma value may be less than about 2.5, about 2, or about 1.5. These methods have been used to produce very dark antique/black pearl interference pigments. The darkest color achieved based on a 5% pigment drawdown in a nitrocellulose varnish is in the range of about 29 to about 32 in terms of lightness value (L* value in CIE1976 color space, measured using a 10 degree observer, illuminant D65 with Specular Component Included), which is very close to the reference LENETA card black (L*=28) along with a very low chroma (typically less than 3). Titan® ST is the range of L*=64 to 65, Engelhard's Cloisonné NU-Antique Series is in the range of L*=37 to 60. In all cases, these are much lighter and less lustrous than the pigment formed by this process.

The methods described may produce pigments with better hiding power while maintaining a high luster. The pigments may have better stability than current pigments at high and low pH, and are less likely to bleed.

In one embodiment the pearlescent pigment is an inorganic material and the ΔE* of the alkaline stability for a homogeneous coating of the pigment, measured over a white background, is less than about 2.

In one embodiment the pearlescent pigment is an inorganic material and the ΔE* of the acid stability for a homogeneous coating of the pigment, measured over a white background, is less than about 4.

In one embodiment the pearlescent pigment is an inorganic material and the ΔE* of magnetically aligned and non-aligned homogeneous coatings of the pigment, measured over a white background, is not less than 20.

In one embodiment the pearlescent pigment has a magnetic susceptibility of about 0.1×10⁻⁵ to 7.5×10⁻⁵ m³/kg.

The pigments may be magnetic or exhibit magnetic susceptibility. In fluid-based systems, such as liquid coatings or uncured plastic preparations containing these pigments, an applied magnetic field may be used to align pigments in specific regions of the coating to create images that appear to be three-dimensional. After the pigments have been aligned, the coating may be cured to solidify the image.

The three-dimensional effect is produced by the pigment particles aligned at non-parallel or intermediate angles with respect to the coating surface. In an applied electric field, the high aspect ratio platelets will align themselves such that the longest dimension of the platelet (namely, the platelet width) aligns itself along the magnetic field lines. The ability to reorient the colored particles allows them to be manipulated to specific angles resulting in a controlled three-dimensional appearance. In regions of where the field lines are perpendicular to the observer, the platelet particles will be perpendicular to the observer resulting in a jet black appearance. This extremely dark appearance is due to light scattering at the particle edges and the absence of a reflective surface. In regions devoid of an applied magnetic force, the particles align more substantially parallel to the applied coating surface resulting in the intensely colored appearance. Applying a magnetic field parallel to the coating surface will orient more of the pigments parallel to the surface resulting in a even more intensely colored appearance.

In one embodiment a cosmetic composition contains the pearlescent pigment. The cosmetic composition may be useful for make-up products for the skin, the eyes, or hair. Examples of compositions intended as make-up for the skin include eye shadows, eye liners, mascaras, body or face powder, foundations, blushes, colored creams, nail polish, lipsticks, lip gloss, hair or body gel, hair or body wash, cover sticks, lotion, concealer and foundation. Examples of cosmetic applications involving the lip area, are lip gloss, lipstick, and other lip compositions. Nail polish may be referred to as nail varnish, or nail enamel.

Pearlescent pigments may be used to produce a makeup cosmetic as described in U.S. Pat. No. 6,663,852, U.S. Pat. No. 6,451,294, and U.S. Pat. No. 6,280,714.

In one embodiment, the pigments of the composition are aligned during or after application of the composition. An example of aligning the pigments of the composition is by applied the composition with a magnetic applicator. The magnetic applicator may be used to align the magnetic particles in the cosmetic allowing control of their appearance.

General cosmetic compositions may contain preservatives, stabilizers, neutralizing agents, aqueous-phase thickeners (polysaccharide biopolymers, synthetic polymers) or fatty-phase thickeners, such as clay minerals, fillers, perfumes, hydrophilic or lipophilic active substances, surfactants, antioxidants, film-forming polymers and mixtures thereof. The amounts of these various ingredients are those conventionally employed in the fields in question and, for example, may be from 0.01 to 30% of the total weight of the composition. In one embodiment, the cosmetic composition may further comprise a binder wherein the pigment represents about 0.5% to about 99.5% of the composition.

Lip cosmetic composition may comprise any ingredient usually used in the field concerned, such as water, preferably in an amount ranging from 0 to 95% of the total weight of the composition, water-soluble or liposoluble dyes, antioxidants, essential oils, preserving agents, fragrances, neutralizing agents, liposoluble polymers, in particular hydrocarbon-based polymers such as polyalkylenes or polyvinyl laurate, gelling agents for an aqueous phase, gelling agents for a liquid fatty phase, waxes, gums, surfactants, additional cosmetic or dermatological active agents such as, for example, emollients, moisturizers (for example glycerol), vitamins, liquid lanolin, essential fatty acids, lipophilic or hydrophilic sunscreens, and mixtures thereof. The composition may also contain lipid vesicles of ionic and/or nonionic type. These ingredients (other than the water) may be present in the composition in a proportion of from 0 to 20% of the total weight of the composition.

In one embodiment a coating or ink composition contains the pearlescent pigment. In another embodiment an article comprises the pearlescent pigment. A coating, ink, or article may further comprise a binder, wherein the pigment represents about 0.5% to about 99.5% of the composition, about 0.1% to about 70%, or about 0.2% to about 10%.

The coating or ink may be printing ink, surface coating, coatings for laser marking, pigment preparation, dry preparation, food colorant, textile coating, architectural coating, synthetic fiber, or fiber based product. A coating may be applied to an object as a liquid, vapor, or solid. Examples of methods for applying a coating are by printing, painting, polymeric coating, or spraying. The coating may be a powder, enamel, aerosol, paint, epoxy, or polymer.

The ink may be a magnetic toner. An example of a magnetic toner is one that is used for Magnetic Ink Character Recognition (MICR). These toners may be used to print security codes on checks and are read by low-cost readers. Many of the toners used for MICR are black. The color and magnetic susceptibility of the MICR ink may be adjusted by using different pearlescent pigments.

The arts of making coatings and inks, as well the various printing processes (i.e., intaglio, flexo, screen, offset, gravure) are very well known in the literatures, so it is not repeated here [see “The Printing Ink Manual”, 5^(th) edition, R. H. Leach, ed. Taylor & Francis, Inc.]. Other less common printing processes include digital offset solutions such as the Hewlett-Packard Indigo presses.

Besides the topical applications such as printings or coatings, the pigments can be incorporated directly into substrates during the formation stage to make an article. For example, to a papers, the pigments can be introduced along with other regular paper fillers such as calcite, talc during paper making to fill the open pores of paper near the surface. If the article is a plastic, the pigment can be introduced during the extrusion of substrate. Examples of articles are plastic, glass, ceramic material, concrete, pressed wood, pills, paper, toothpaste, food products, or agricultural products.

The terms goniochromatic, iridescent, and pearlescent, may be used interchangeably to mean a change of color depending on the viewing angle.

Unless otherwise specified, the alkaline stability of a pigment is measured as ΔE* measured against a white background, using the procedure described in Example 32.

Unless otherwise specified, the acid stability of a pigment is measured as ΔE* measured against a white background, using the procedure described in Example 33.

Unless otherwise specified, the HPI, CIELAB coordinates, hue angle, h_(ab), L*, a*, b*, and chroma of a pigment are measured using the pigment drawdown described in Example 32 with a white or black background using a D65 illuminant and a 10 degree observer.

A homogeneous coating of a pigment is a coating that only contains one colored element, it is not a blend of colored elements. An example of a pigment that will not form a homogeneous coating is Cloisonné® Nu Antique Gold pigment, the pigment contains both color pigment and iron oxide.

EXAMPLES Example 1 FeCl₃-Urea Homogenous Hydrolysis Process for Depositing an Easily Reducible FeOOH Layer

-   -   A 0.1M HCl solution (356.9 g) was added to a 500 ml cylindrical         reaction vessel blade (for gentle stirring and non-sticking         property). The solution was stirred at 175 RPM. A 7.1 g 45% wt         FeCl₃ Stock Solution (Riedel 12322, 45% wt FeCl₃, 55% water) was         add drop-wise into the reactor.     -   Urea (16 g) was added slowly into reactor under agitation.     -   Sky Chemical Russet Pigment (20 g) was added to the reactor, and         stirred for 5 minutes.     -   The temperature was increased 2° C./min to 80° C. and held for 4         hour.     -   The pigment is recovered by filtration and washed with distilled         water.

Example 2 Solid-on-Solid Catalytic Aqueous-Phase Hydrogenation Process

Step 1—Wet Micronization of Catalyst

-   -   Platinum oxide powder (200 mg, 10-50 micron grade,         Aldrich 206032) was stirred in 100 g PEG 400 (i.e., 2 mg PtO2/g         fluid).     -   The slurry was loaded into a Eiger-Mill equipment with 0.5 mm         zirconia media and water cooling jacket. The power was set to         maximum and ran for 6 hours. The final slurry was a greenish         black and did not settle for about 1 to 2 days.     -   The particle size was checked with dynamic light scattering         (Horiba DLLS Particle Sizer) and OM (optical microscope, Nikon)         to ensure no particles larger than 1 micron were left.

Step 2—Hydrogenation

-   -   PEG 400 (100 g), FeOOH (20 g) coated red pearl pigment (i.e.,         Sky Chemical Super Russet) and 3 g of the micronized PtO₂ slurry         (2 mg catalyst/g fluid) from step 1, was loaded into a         steel-constructed hydrogenation chamber.     -   An agitator was lowered into the chamber. The chamber was closed         and connected to the H₂ reservoir.     -   The gas line was purged several times with N₂.     -   The chamber was pressurized with H₂ to roughly 10-14 bar.     -   The agitator was turned on and the heating mantle was set to         200° C. The reaction was run for 6 hours.     -   The heating mantle was removed to let the chamber cool. The         chamber head space and lines were purged with N₂ gas to remove         any residual H₂.     -   The chamber was opened and the slurry was poured out into a         container.

Step 3—Catalyst Recovery and Pigment Wash

-   -   The slurry was settled in the container. The pearl pigment will         sink to the bottom much faster than colloidal PtO₂. As soon as         the majority of the pigment settled, the supernatant was         decanted, which was rich in PtO₂, and put aside for reuse.     -   The settled pigments were then washed several times with water         and one time with industrial alcohol on a mesh filter (20 micron         mesh) to remove the PEG and residual colloidal PtO₂.     -   The pigment was dried under mild vacuum.

Example 3 Preparation of Homogenous Platinum Colloidal Nanoparticle Catalyst

-   -   Polyvinylpyrrolidone (PVP) Reductant Solution: Anhydrous         ethylene glycol (80 g) and K15 PVP (10 g, Fluka 81390 or ISP)         were mixed at 3000 RPM with a Hauschild mixer until dissolved.         The mixture was added to a 1 L 3.5″ Teflon Coated Cylindrical         reactor with a 2″ PTFE coated 3-leaf blade, and a nitrogen         purging line.     -   Precursor Solution: Anhydrous ethylene glycol (80 g) and         H₂PtCl₆-6H₂O salt (0.5 g, SA C3044) were added to a 4 oz jar         with a magnetic stir bar, and stirred until dissolved. The         liquid was sonicated for 10 minutes to remove oxygen then added         to the PVP reductant solution.     -   Mixing of Precursor and Reductant: Anhydrous ethylene glycol         (80 g) was added to the reaction vessel, followed by agitation         at roughly 200 RPM to gently mix precursor with reductant at         room temperature. The N₂ purging line was lowered to just below         the liquid surface to provide an insert gas blanket.     -   Thermal Activation: The mixture was heated from approximately         20° C. to 120° C. in roughly 100 minutes. The mixture was held         at 120° C. for 1 hour before switching off the heat. The         solution was allowed to cool in the oil bath back to room         temperature.     -   Recovery: The Pt-in-(PVP+EG) liquid [0.75 mg Pt/q-fluid] was         poured into a glass jar and the jar was sealed.

Example 4 Liquid-Phase Hydrogenation Process with a Homogenous Catalyst

Step 1—Hydrogenation

-   -   PEG 400 (100 g), FeOOH coated red pearl pigment (20 g, i.e., Sky         Chemical Super Russet), and Pt colloidal solution (8 g) from         Example 3 (300 ppm level of Pt, normalized to dry content of         pigment) was loaded into a steel-constructed hydrogenation         chamber.     -   An agitator was lowered into the chamber. The chamber was closed         and connected to the H₂ reservoir.     -   The gas line was purged several times with N₂.     -   The chamber was pressurized with H₂ to roughly 10-14 bar.     -   The agitator was turned on and the heating mantle was set to         200° C. The reaction was run for 6 hours.     -   The heating mantle was removed to let the chamber cool. The         chamber head space and lines were purged with N₂ gas to remove         any residual H₂.     -   The chamber was opened and the slurry was pour out into a         container.

Step 2—Catalyst Recovery and Pigment Wash

-   -   After the slurry was allowed to settle in a container, the         supernatant fluid was discarded.     -   The settle pigments were then washed several times with 10% PVP         in water and one time with industrial alcohol on a mesh filter         (20 micron mesh) to remove PEG and residual colloidal Pt.     -   The pigment was dried under mild vacuum

Example 5 Onyx Black Pearlescent Pigment

Step 1—FeOOH Deposition by FeCl₃-Urea Homogenous Hydrolysis

-   -   A 0.1M HCl solution (10,707 g) was added to a 15 L cylindrical         reaction vessel. The solution was stirred at 175 RPM. A 213 g         FeCl₃ Stock Solution (Riedel 12322, 45% wt FeCl₃, 55% water) was         added drop-wise into the reactor.     -   Urea (1440 g) was added slowly into reactor under agitation.     -   Sudarshan Russet Pigment (600 g) was added to the reactor, and         stirred for 5 minutes. This deposition technique is not         exclusive to the Sudarshan Russet pigment. Other platelet-like         substrates may be used including those comprising synthetic mica         (uncoated or metal oxide coated) or flaky glass supports. These         substrates may contain multiple adsorbed layers, such as those         that contain materials of varying refractive index. It is         important to note that equivalent levels of Fe uptake (g Fe/g         mica) can be achieved using both pre-coated or uncoated supports         by either redeposition or by adjustment of the reaction         conditions.     -   The reaction temperature was increased 2° C./min to 90° C. and         held for 4 hour.     -   The coated pigment was then recovered by vacuum filtration using         a 10 micron filter. The filter cake was washed three times with         5 L of water. The coated pigment was then dried at 60° C.         overnight.

Step 2—Hydrogenation

-   -   PEG 400 (1920 g), FeOOH coated red pearl pigment (400 g, i.e.,         Sudarshan Russet), and Pt colloidal solution (80 g) from Example         3 was loaded into a steel-constructed hydrogenation chamber.     -   An agitator was lowered into the chamber. The chamber was closed         and connected to the H₂ reservoir.     -   The gas line was purged several times with N₂.     -   The chamber was pressurized with H₂ to roughly 340-380 psig.     -   The agitator was turned on and the heating mantle was set to         200° C. The reaction was run for 6 hours.     -   The heating mantle was then removed to let the chamber cool. The         chamber head space and lines were purged with N₂ gas to remove         any residual H₂.     -   The chamber was opened and the slurry was poured out into a         container.     -   The hydrogenated pigment was then recovered by vacuum filtration         using a 10 micron filter. The filter cake was washed with 4 L of         water followed by 2 L of ethanol.     -   The pigment was then placed in an oven at 60° C. for 24 hours.

Step 3—Pigment Drawdown Preparation

-   -   The hydrogenated pigment (0.5 g) was dispersed in 4.5 g of PPG         Delstar PMR499 acrylic enamel in a max 15 translucent jar         designed for the DAC150FVZ-K model (Hauschild Engineering) high         speed mixer.     -   Glass beads (2 g) were added to the dispersed suspension.     -   The pigment suspension (10% pigment) was then mixed for 3         minutes at 3000 rpm using a DAC150FVZ-K model high speed mixer.     -   Three preparations of the same 10% pigment suspension were         prepared using the procedure described above. Directly following         mixing, each pigment suspension was applied to a Form 2C Leneta         card using either a 1.5, 3 or 6 mil Bird applicator.     -   Each drawdown was allowed to dry at room temperature for 30         minutes and then placed in an oven at 60° C. for an additional         30 minutes.     -   The colorimetric parameters (CIE L*a*b*) of the dried films were         measured using a 10 degree observer and D65 illuminant (specular         component included and specular component excluded) against both         a white and black reference background. The results of these         measurements are listed in the tables below.

TABLE 1 Colorimetric parameters (CIE L*a*b*) of Onyx black (Example 5) drawdowns (10% pigment) using a 10 degree observer and D65 illuminant with specular component included (SCI) at varying film thickness with a black background reference. Sample Over Black Background Uncoated Black Background Thickness L* a* b* C* H L* a* b* C* h 1.5 mil 29.34 1.01 −1.82 2.08 299.03 27.32 0.32 −0.01 0.32 357.88 3.0 mil 29.75 1.58 −2.16 2.68 306.14 27.40 0.35 −0.07 0.35 349.26 6.0 mil 28.89 1.29 −2.03 2.41 302.5 27.19 0.27 −0.19 0.33 325.25

TABLE 2 Colorimetric parameters (CIE L*a*b*) of Onyx black (Example 5) drawdowns (10% pigment) using a 10 degree observer and D65 illuminant with specular component included (SCI) at varying film thickness with a white background reference. Sample Over White Background Uncoated White Background Thickness L* a* b* C* H L* a* b* C* h 1.5 mil 43.14 1.21 −0.70 1.40 329.97 93.36 −0.80 3.23 3.33 103.89 3.0 mil 30.87 1.57 −1.89 2.46 309.78 93.41 −0.77 3.18 3.27 103.64 6.0 mil 28.88 1.27 −2.03 2.39 301.93 93.44 −0.63 3.33 3.39 100.76

TABLE 3 Colorimetric parameters (CIE L*a*b*) of Onyx black (Example 5) drawdowns (10% pigment) using a 10 degree observer and D65 illuminant with specular component excluded (SCE) at varying film thickness with a black background reference. Sample Over Black Background Uncoated Black Background Thickness L* a* b* C* H L* a* b* C* h 1.5 mil 11.17 1.71 −2.48 3.01 304.59 8.15 1.03 1.85 2.12 60.92 3.0 mil 13.89 2.82 −2.94 4.07 313.8 7.90 1.17 2.15 2.45 61.59 6.0 mil 14.88 2.27 −2.62 3.46 310.90 8.12 0.93 1.72 1.95 61.62

TABLE 4 Colorimetric parameters (CIE L*a*b*) of Onyx black (Example 5) drawdowns (10% pigment) using a 10 degree observer and D65 illuminant with specular component excluded (SCE) at varying film thickness with a white background reference. Sample Over White Background Uncoated White Background Thickness L* a* b* C* H L* a* b* C* h 1.5 mil 36.28 1.02 0.09 1.02 4.79 91.74 −0.80 3.30 3.39 103.65 3.0 mil 16.84 2.61 −2.28 3.47 318.85 91.58 −0.77 3.33 3.42 103.07 6.0 mil 15.14 2.36 −2.70 3.59 311.05 91.69 −0.75 3.26 3.34 103.03

Example 6 Neon Green-Gold Pearlescent Pigment

A mixture of HCl (706.2 g of 0.1 M solution), FeCl₃ (14.2 g of 45 wt % solution), urea (96 g), and TiO₂ coated natural mica pigment (40 g, SunPearl Iridescent Green, 10-60 μm particle size) was charged into a 1 L jacketed pot reactor under agitation at 180 rpm. The mixture had a pH of approximately 1.8. The mixture was then heated to 90° C. The pigment is complete when urea decomposition resulted in a rise of the solution pH to between about 6.3 and 6.5. After about 2 hours at 90° C., the pigment was filtered, rinsed with deionized water, and dried at 60-80° C. A neon-like lustrous pigment having a green interference color combined with a golden yellow absorbance color was obtained. The resulting pigment contained approximately 6.5 wt % elemental iron as measured using a Perkin Elmer 5100 PC Atomic Absorption Spectrophotometer. CIELAB values measured for this pigment and the starting substrate with a Spectraflash SF600 Plus spectrophotometer are listed in Table 5.

Example 7 Neon Gold Pearlescent Pigment

A neon gold pearlescent pigments was prepared via the same technique demonstrated in Example 1, except the amount of each reagent initially charged to the reaction vessel is different as depicted in Table 6. As shown in Table 6, the amount of FeCl₃ used for coating was twice that used in Example 1 with the same Urea/Fe molar ratio of 40.6 and the same starting substrate. Following filtration, washing, and drying, a neon-like lustrous pigment having a golden interference color was obtained (see Table 5 for CIELAB values). The resulting pigment contained approximately 10.7 wt % elemental iron.

This example illustrates thicker coatings of FeOOH layers on TiO₂-coated platelet-like substrates can be utilized to progress the interference color to the next shade. This is evident by comparison of the hue angle measured over a black background (see Table 5) for the coated substrates and the starting material. The uncoated substrate has a green interference color with a hue angle of 205.1. FeOOH coating progresses the hue angle clockwise with increasing thickness. As shown for a reaction Fe/pigment mass ratio of 0.055 (or 6.5 wt % Fe in the final pigment), the hue angle progresses from a green interference color (hue angle=205.1) to a green-gold interference color (hue angle=108.6). At about double the reaction Fe/pigment mass ratio (which results in 10.7 wt % Fe in the final pigment), the hue angle further progresses to a more golden interference color (hue angle=83.0).

Increased FeOOH deposition results in a darkening of the substrate, or a drop in the L* value, as shown in Table 5. The L* value of the starting material with both white and black backgrounds is reduced as the Fe/pigment mass ratio used in deposition is increased.

TABLE 5 CIE Lab values measured for Examples 6 and 7 using a 10° observer and D65 illuminant with specular component included. Pigment drawdowns (3 mil Bird applicator) were prepared by dispersing 0.75 g pigment in 5 g of vehicle (10% CAB 531-1 (Eastman Chemical) in n-butyl acetate). Reaction Final White Background Black Background Fe/Pigment Interference L* a* b* Hue L* a* b* Hue Example Ratio (g/g) Color value value value Chroma Angle value value value Chroma Angle SunPearl 0 Transparent 92.8 −2.3 5.6 6.0 112.5 79.9 −12.7 −6.0 14.0 205.1 Iridescent Green Green 6 0.055 Transparent 78.2 3.7 35.5 35.5 84.1 72.8 −9.2 27.5 29.0 108.6 Green/Gold 7 0.110 Transparent 74.7 12.4 46.9 48.5 75.2 68.4 4.7 38.3 38.6 83.0 Gold

TABLE 6 Quantity of reagents used for Fe(OH)₃ deposition on commercially-available TiO₂-coated natural mica substrates. Initial Reaction Solution Composition Example Substrate Brand Name Pigment (g) 45 wt % FeCl₃ (g) Urea (g) 0.1 M HCl (g) 6 SunPearl Iridescent Green 40 14.2 96 706.2 7 SunPearl Iridescent Green 40 28.4 192 706.2 10 SunPearl Iridescent Gold 40 14.2 96 706.2 11 SunPearl Iridescent Gold 40 28.4 192 706.2 14 SunPearl Iridescent Red 40 3.55 24 706.2 15 SunPearl Iridescent Red 40 7.1 48 706.2 16 SunPearl Iridescent Red 40 14.2 96 706.2 20 SunPearl Iridescent Violet 40 14.2 48 706.2 21 SunPearl Iridescent Violet 40 28.4 192 706.2 24 SunPearl Iridescent Blue 40 14.2 48 706.2 25 SunPearl Iridescent Blue 40 28.4 192 706.2

Example 8 Lustrous, Semi-Opaque Green Pearlescent Pigment

The pigment prepared in Example 6 (20 g, Mica+TiO₂+Fe(OH)₃, particle size of 10-60 μm) and PVP stabilized Pt catalyst (4 g) in ethylene glycol (prepared in Example 3) were dispersed in polyethylene glycol 400 (96 g, PEG 400, EMD Chemical, CAS 25322-68-3), and added to a 600 mL steel Parr reactor equipped with twin 45 degree pitch blade impellers. The mixture was agitated at approximately 800 rpm. The reaction solution was purged several times by pressurizing the vessel with nitrogen and then evacuating under vacuum. Following sufficient purging, the mixture was heated to 220° C., pressurized with hydrogen to 10.3 bar and held at these conditions for 6 hours. The pigment was filtered, rinsed with 4 L deionized water followed by 1 L ethanol, and dried at 60-80° C. A deep and intensely colored, semi-opaque, green pearlescent pigment (see Table 7 for corresponding CIE Lab color values) was obtained.

The weight fraction of Fe(II) and Fe(III) in the final pigment is given in Table 8. Total iron and Fe(II) content was determined via atomic absorption spectroscopy and oxidation/reduction titration with 0.1 N potassium dichromate, respectively. The hydrogenation resulted in reduction of approximately 15.4% of the deposited iron (Fe(III) to Fe(II)).

As shown in Table 7, this reduction process transformed the bichroic starting material (Example 6) into a more opaque pigment with more uniform color coordinates as measured with white and black backgrounds. The level of opacity, or hiding power can be described using a hiding power index (HPI) defined as:

$\begin{matrix} {{HPI} = \frac{1}{{{L^{*}({black})} - {L^{*}({white})}}}} & (3) \end{matrix}$

where L*(black) and L*(white) are the measured lightness or L* value on a black and white background, respectively. Full opacity is obtained when L*(black) is equivalent to L*(white) causing the hiding power index to equate to infinity. The HPI associated with this pigment is listed in Table 7.

TABLE 7 CIE Lab values measured for Examples 8 and 9 using a 10° observer and D65 illuminant with specular component included. Pigment drawdowns (3 mil Bird applicator) were prepared by dispersing 0.75 g pigment in 5 g of vehicle (10% CAB 531-1 (Eastman Chemical) in n-butyl acetate). Reaction Final White Background Black Background Fe/Pigment Interference L* a* b* Hue L* a* b* Hue Example Ratio (g/g) Color HPI value value value Chroma Angle value value value Chroma Angle SunPearl 0 Transparent 0.078 92.8 −2.3 5.6 6.0 112.5 79.9 −12.7 −6.0 14.0 205.1 Iridescent Green Green 8 0.055 Semi- 1.56 61.9 −10.2 20.1 22.6 116.8 61.3 −11.7 19.4 22.6 121.1 Opaque Green 9 0.110 Opaque 50.0 48.3 5.8 22.8 23.5 75.7 48.3 5.6 22.7 23.4 76.0 Gold

TABLE 8 Total composition of Fe(II) and Fe(III) measured for Examples 8 and 9. Total Fe Fe(II) Fe(III) Fe(II)/Total Fe Fe(III)/Total Example (g/g) (g/g) (g/g) (g/g) Fe (g/g) 4 0.065 0.01 0.055 0.15 0.85 5 0.107 0.017 0.09 0.16 0.84

Example 9 Lustrous, Opaque Gold Pearlescent Pigment

An intensely colored, gold pearlescent pigments with increased opacity relative to Example 8, was prepared according to the procedure for Example 8 except that the Fe/Pigment mass ratio used in deposition was increased by two-fold resulting in higher weight fraction of Fe in the final pigment (see Tables 7 and 8). As shown by the CIELAB values listed in Table 7, a vibrantly colored gold pearlescent pigment was obtained following hydrogenation. The resulting pigment has higher opacity, or higher hiding power index relative to Example 8 (50.0 compared to 1.56 for Example 3) as shown in Table 7.

The progression of the interference color of TiO₂-coated platelet like substrates and the opacity may be precisely controlled by the Fe/pigment mass ratio. As will be shown in the following examples, the two-step process (coating and reduction) may be applied to TiO₂ coated mica pigments with various interference colors such as: gold, red, violet, blue, green, and silver. An infinite number of lustrous, colored pearlescent pigments that span all four quadrants of the CIELAB color coordinate system may be produced while controlling the opacity to suit the intended application.

The color and opacity is directly controlled by the thickness of both the initial TiO₂ and the deposited FeOOH layers. For semi-opaque shades (as described in Example 8), the reduction of thin FeOOH layers result in pigments characterized by a simple progression of the initial interference color or hue angle as shown in Table 7. Reduction of thicker FeOOH layers results in further advancement of the interference color or hue angle and can progress the interference color to the next shade (in the case of Example 5, from green to yellow) while increasing the opacity or HPI.

Examples 10 Through 13 Development of Lustrous, Pearlescent Pigments Using TiO₂-Coated Mica with a Gold Interference Color

The methods described above may be applied to TiO₂-coated mica substrates characterized by a yellow or gold interference color. Examples 10 and 11 are analogous to 6 and 7, except that that the substrate material used was SunPearl Iridescent Gold (10-60 μm) rather than SunPearl Iridescent Green. The composition of the reaction solution for both Example 10 and 11 is shown in Table 6 with the CIELAB values of the resulting pigments given in Table 9.

As shown previously, FeOOH deposition results in clockwise advancement of the hue angle (over a black background) of the starting substrate (see Table 9). The initial gold interference color (hue angle=93.4) is advanced to orange gold (Example 6, hue angle=68.6) at low Fe loading and further to pink (hue angle=24.2) at increased FeOOH layer thickness. Following deposition, these pigments are goniochromatic, or characterized by a specific interference color (in this case, orange, gold, or pink) at some viewing angles, with a gold to yellow absorbance color at others. The gold to yellow absorbance color is due to the precipitated yellow iron oxide or FeOOH layer. As the FeOOH thickness increases, the darkness of the coated pigment increases as shown by the measured L* values depicted in Table 9.

The reduction of Examples 10 and 11 by the hydrogenation method described in Example 8, yielded Examples 12 and 13, respectively. Example 12 is a lustrous semi-opaque, orange pigment with a HPI of 0.267. Due to the relatively thin FeOOH layer, reduction resulted in a small advancement of the hue angle, shifting the interference color from gold to orange. Although the conditions for reduction between Examples 12 and 13 were equivalent, Example 13 yields a more opaque (HPI=1.099), darker, lustrous plum pigment. The larger color shift, from a hue angle of 49.2 (Example 12 on a black background) to 354.7 (Example 13 on a black background), and the increase in opacity is due to the increased thickness of the coated FeOOH layer.

TABLE 9 CIE Lab values measured for Examples 10-13 using a 10° observer and D65 illuminant with specular component included. Pigment drawdowns (3 mil Bird applicator) were prepared by dispersing 0.75 g pigment in 5 g of vehicle (10% CAB 531-1 (Eastman Chemical) in n-butyl acetate). Reaction Final White Background Black Background Fe/Pigment Interference L* a* b* Hue L* a* b* Hue Example Ratio (g/g) Color HPI value value value Chroma Angle value value value Chroma Angle SunPearl 0 Transparent 0.094 93.3 −1.3 9.6 9.69 97.9 82.59 −1.0 17.6 17.6 93.4 Iridescent Gold Gold 10 0.055 Transparent 0.118 76.8 16.2 46.8 49.6 70.9 68.4 14.3 36.4 39.1 68.6 Orange- Gold 11 0.110 Transparent 0.091 67.0 26.7 29.1 39.5 47.5 56.0 24.2 10.9 26.5 24.2 Pink 12 0.055 Semi- 0.267 59.6 28.9 34.8 45.2 50.3 55.9 25.6 29.7 39.2 49.2 Opaque Orange 13 0.110 Semi- 1.099 37.9 15.6 −0.5 15.6 358.0 37.0 14.9 −1.4 15.0 354.7 Opaque Plum

Examples 14 Through 19 Development of Lustrous, Pearlescent Pigments Using TiO₂-Coated Mica with a Red Interference Color

Examples 14 through 19 were prepared according to the procedure described in Example 6, except that the TiO₂-coated mica substrates (SunPearl Iridescent Red, 10-60 μm) were characterized by a pink to red interference color. The reaction Fe/Pigment mass ratios used are indicated in Table 6. The CIELAB values for each pigment prepared are shown in Table 10.

For clarity, the a* and b* coordinates of Examples 14-16 measured against a black background are plotted in FIG. 1. Pigment drawdowns (3 mil Bird applicator) of Examples 14-16 were prepared by dispersing 0.75 g pigment in 5 g of vehicle (10% CAB 531-1 (Eastman Chemical) in n-butyl acetate). FIG. 1 shows that deposition at very low Fe/pigment ratios, in particular for Fe/pigment ratios less than about 0.055, results in an initial increase in the b* coordinate with small impact on the a* value. This is perhaps due to the characteristic yellow absorbance of FeOOH. It is from this point, point 2 in FIG. 1, that the clockwise shift in hue angle begins at increasing FeOOH layer thickness. As shown, the hue angle begins to progress pass the initial hue angle of the support material at Fe/pigment ratios of about 0.055. For Example 16 (Fe/pigment ratio=0.055), the interference color is noticeably violet indicating sufficient progression to the next shade (red to violet).

The reduction of Examples 14-16 by the hydrogenation method described in Example 8, yielded Examples 17-19, respectively. As shown by the CIELAB values depicted in Table 10, reduction yields lustrous, pearlescent pigments ranging from pink to light violet, and the hiding power index, or HPI, associated with these pigments increased with increasing Fe/pigment mass ratio.

TABLE 10 CIE Lab values measured for Examples 14-19 using a 10° observer and D65 illuminant with specular component included. Pigment drawdowns (3 mil Bird applicator) were prepared by dispersing 0.75 g pigment in 5 g of vehicle (10% CAB 531-1 (Eastman Chemical) in n-butyl acetate). Reaction Final White Background Black Background Fe/Pigment Interference L* a* b* Hue L* a* b* Hue Example Ratio (g/g) Color HPI value value value Chroma Angle value value value Chroma Angle SunPearl 0 Transparent 0.047 91.9 1.14 4.36 4.51 75.3 70.7 17.3 −6.6 18.5 339.3 Iridescent Pink/Red Red 14 0.01375 Transparent 0.069 83.2 11.9 21.6 24.7 61.2 68.8 17.3 3.0 17.5 9.8 Pink 15 0.0275 Transparent 0.073 79.4 17.0 21.1 27.1 51.0 65.7 18.7 1.6 18.8 4.8 Pink 16 0.055 Transparent 0.059 70.7 23.1 12.7 26.4 28.8 53.7 19.1 −14.5 24.0 322.8 Pink-Violet 17 0.01375 Transparent 0.068 72.6 23 15.3 27.6 33.6 58.0 26.2 −4.9 26.6 349.4 Pink 18 0.0275 Transparent 0.095 63.4 31.5 9.5 32.9 16.8 52.9 27.8 −6.9 28.7 346.2 Pink 19 0.055 Semi- 0.305 47.7 18.2 −12.9 22.3 324.6 44.4 18.4 −17.4 25.3 316.6 Opaque Light Violet

Examples 20 Through 23 Development of Lustrous, Pearlescent Pigments Using TiO₂-Coated Mica with a Violet Interference Color

Examples 20 and 21 were prepared according to the procedure described in Example 6, except the TiO₂-coated mica substrate had a violet interference color (SunPearl Iridescent Violet, 10-60 μm), and used reaction Fe/pigment ratios of 0.055 and 0.110, respectively as shown in Table 6. The CIELAB values for the pigments following FeOOH deposition are given in Table 11.

TABLE 11 CIE Lab values measured for Examples 20-23 using a 10° observer and D65 illuminant with specular component included. Pigment drawdowns (3 mil Bird applicator) were prepared by dispersing 0.75 g pigment in 5 g of vehicle (10% CAB 531-1 (Eastman Chemical) in n-butyl acetate). Reaction Final White Background Black Background Fe/Pigment Interference L* a* b* Hue L* a* b* Hue Example Ratio (g/g) Color HPI value value value Chroma Angle value value value Chroma Angle SunPearl 0 Transparent 0.047 91.2 1.4 2.5 2.9 60.2 69.7 17.7 −16.7 24.3 316.7 Iridescent Violet Violet 20 0.055 Transparent 0.064 74.9 16.7 12.6 20.9 37.07 59.3 6.1 −13.1 14.5 295.0 Violet 21 0.110 Transparent 0.096 72.8 8.6 21.6 23.3 68.4 62.4 −11.4 4.3 12.2 159.4 Blue 22 0.055 Semi- 0.532 44.2 3.9 −21.1 21.5 280.4 42.3 2.0 −23.9 24.0 274.8 Opaque Dark Violet 23 0.110 Opaque 4.762 43.5 −10.4 −5.5 11.8 208.0 43.3 −10.8 −6.04 12.4 209.24 Dark Blue

The pigments of Examples 20 and 21 displayed the characteristic clockwise shift in hue angle, resulting in the gradual progression from a violet to blue interference color at increased Fe/pigment ratio. The reduction of Examples 20 and 21, using the conditions described in Example 8, yielded Examples 22 and 23, respectively. As shown in Table 11, the reduction of thin FeOOH surface layers (such as Example 22) yields a semi-opaque pearlescent pigment characterized by a color similar to the interference color of the TiO₂-coated mica support. In this case, Example 22 yields a lustrous, dark violet pearlescent pigment. Reduction of thicker FeOOH layers, such as the pigment produced in Example 23, results in an advancement of the interference color to the next shade (in this case from violet to blue) and increased opacity or HPI.

Examples 24 Through 27 Development of Lustrous, Pearlescent Pigments Using TiO₂-Coated Mica with a Blue Interference Color

Examples 24 and 25 were prepared according to the procedure described in Example 6, except the TiO₂-coated mica substrate had a blue interference color (SunPearl Iridescent Blue, 10-60 μm), and used reaction Fe/pigment ratios of 0.055 and 0.110, respectively, as shown in Table 6. The CIELAB values are given in Table 12.

TABLE 12 CIELAB values measured for Examples 24-27 using a 10° observer and D65 illuminant with specular component included. Pigment drawdowns (3 mil Bird applicator) were prepared by dispersing 0.75 g pigment in 5 g of vehicle (10% CAB 531-1 (Eastman Chemical) in n-butyl acetate). Reaction Final White Background Black Background Fe/Pigment Interference L* a* b* Hue L* a* Hue Example Ratio (g/g) Color HPI value value value Chroma Angle value value b* value Chroma Angle SunPearl 0 Transparent 0.053 92.2 −1.0 0.9 1.3 137.5 73.2 −7.1 −22.5 23.6 252.5 Iridescent Blue Blue 24 0.055 Transparent 0.103 76.7 5.9 15.7 16.8 69.37 67.0 −15.8 −0.2 15.8 180.6 Blue 25 0.110 Transparent 0.173 71.4 5.6 35.3 35.7 81.1 65.6 −9.51 25.9 27.6 110.2 Green Gold 26 0.055 Semi- 0.520 60.3 −8.5 1.2 8.6 171.7 58.4 −17.0 −3.4 17.4 191.3 Opaque Turquoise 27 0.110 Opaque Olive 2.170 49.5 −9.9 13.4 16.6 126.4 49.1 −10.1 12.8 16.3 128.4 Green

The pigments of Examples 24 and 25 displayed the characteristic clockwise shift in hue angle resulting in the gradual progression from a blue to green interference color at increased Fe/pigment ratio. The reduction of Examples 24 and 25, using the conditions described in Example 6 yielded Examples 26 and 27, respectively. As shown in Table 12, the reduction of thin FeOOH surface layers (such as Example 26) yields a semi-opaque pearlescent pigment characterized by a color similar to the interference color of the TiO₂-coated mica support. In this case, Example 26 yields a lustrous, turquoise pearlescent pigment. Reduction of thicker FeOOH layers, such as the pigment produced in Example 27, results in an advancement of the interference color to the next shade (in this case from an iridescent blue to opaque olive green) and increased opacity or HPI.

The examples described above indicate that an almost infinite number of lustrous, vibrant colored pearlescent shades with controlled opacity may be prepared by the methods described herein. The potential color range spans the CIELAB color space.

Examples 28 Through 31 Development of Lustrous, Pearlescent Pigments Using TiO₂-Coated Mica with a Silver Interference Color

Examples 28 and 29 were prepared according to the procedure described in Example 6, except the TiO₂-coated mica substrate had a silver interference color (SunPearl Silver White, 10-60 μm), and used Fe/pigment ratios of 0.055 and 0.110, respectively, as shown in Table 13. The CIELAB values are given in Table 14.

TABLE 13 Quantity of reagents used for FeOOH deposition on commercially-available TiO₂-coated natural mica substrates. Initial Reaction Solution Composition Pigment 45 wt % Urea 0.1 M Example Substrate Brand Name (g) FeCl₃ (g) (g) HCl (g) 28 SunPearl Silver White 40 14.2 96 706.2 29 SunPearl Silver White 40 28.4 192 706.2

TABLE 14 CIELAB values measured for Examples 28-31 using a 10° observer and D65 illuminant with specular component included. Pigment drawdowns (3 mil Bird applicator) were prepared by dispersing 0.75 g pigment in 5 g of vehicle (10% CAB 531-1 (Eastman Chemical) in n-butyl acetate). Reaction Final White Background Black Background Fe/Pigment Interference L* a* b* Hue L* a* b* Hue Example Ratio (g/g) Color HPI value value value Chroma Angle value value value Chroma Angle SunPearl 0 Transparent 0.136 93.0 −0.1 3.6 3.6 91.2 85.6 −1.5 −2.4 2.9 237.8 Silver Silver White 28 0.055 Transparent 0.232 85.4 6.3 21.5 22.4 73.6 81.0 0.6 14.7 14.7 87.8 Gold-Silver 29 0.110 Transparent 0.376 78.1 8.8 28.5 29.8 72.9 75.5 3.9 24.6 25.0 81.1 Gold 30 0.055 Semi- 0.862 76.7 6.4 21.7 22.6 73.5 75.6 4.4 19.9 20.4 77.5 Opaque Champagne 31 0.110 Opaque 1.852 61.9 1.8 12.6 12.8 81.9 61.4 1.5 12.2 12.3 83.11 Metallic Grey

As shown in Table 14, FeOOH deposition results in a transition from a transparent silver white to golden shades. The deposition of thicker FeOOH layers results in a more golden color and a noticeably darker appearance (lower L* value). The reduction of Examples 28 and 29, using the conditions described in Example 8 yielded Examples 30 and 31, respectively. Example 30 is a lustrous, semi-opaque, champagne-colored pearlescent pigment with a HPI of 0.862. At increased reaction Fe/pigment mass ratio, as used in Example 31, gave a more opaque (HPI=1.852), metallic grey pearlescent pigment with a darker appearance (lower L* value, see Table 14).

Example 32 Alkaline Stability Testing Blue Pearlescent Pigments

Example 23 and six commercially available blue pearlescent pigments were tested for alkaline stability. The samples tested and their corresponding components are listed in Table 15.

TABLE 15 Pigment samples tested for alkaline (pH 12.5) stability. Product Particle Size Sample Supplier Code Composition Range (μm) Example 23 Sun Mica, TiO₂, 10-60  Chemical Fe₃O₄ Duocrome ® BY Engelhard 226C Mica, TiO₂, 6-50 Iron Blue Duocrome ® BR Engelhard 426C Mica, TiO₂, 6-50 Iron Blue Duocrome ® BV Engelhard 526C Mica, TiO₂, 6-50 Iron Blue Duocrome ® BG Engelhard 826C Mica, TiO₂, 6-50 Iron Blue Cosmica ® Blue Engelhard MCB27 Mica, Iron 6-48 Blue Cloisonné ® Blue Engelhard 626C Mica, TiO₂, 6-48 Iron Blue

A basic solution (pH 12.5, NaOH in distilled water) was mixed with 2 wt % pigment (see Table 15) to prepare suspensions. The suspensions were mixed, and allowed to settle for about 5 hours. The pigments were then filtered, rinsed with deionized water, and dried at 80° C.

Pigment drawdowns (3 mil Bird applicator) were prepared by dispersing 0.5 g of each pigment in 4.5 g of vehicle (PPG Delstar DMR499 Acrylic Enamel), followed by applying the mixture to a Leneta Form 2C opacity card. The CIELAB color coordinates (100 observer and D65 illuminant with specular component included) for the treated and untreated samples were measured using a Spectraflash SF600 Plus spectrophotometer at a 90° viewing angle. The hiding power index (before and after treatment) and color difference or ΔE* (ΔE*=((ΔL*)²+(Δa*)²+(Δb*)²)^(1/2)) between the treated and untreated samples were measured against a black and white background, see Table 16.

TABLE 16 Hiding power index (HPI) and color difference values (ΔE*) for blue pearlescent pigment samples before and after alkaline treatment (pH 12.5, 5 hours). ΔE* (Treated vs Untreated) Sample HPI (Untreated) HPI (Treated) White Background Black Background Example 23 0.469 0.408 1.71 1.40 Duocrome ® BY 0.294 0.068 39.66 21.82 Duocrome ® BR 0.110 0.036 46.01 15.29 Duocrome ® BV 0.091 0.033 50.75 13.26 Duocrome ® BG 0.315 0.063 45.99 20.84 Cosmica ® Blue 0.649 0.119 14.23 2.79 Cloisonné ® Blue 0.169 0.039 56.50 16.94

All the commercially available blue pearlescent pigments tested displayed a marked shift in color and opacity following immersion in alkaline solution. The measured color difference is due to the instability of iron blue in alkaline environment. The absence of iron blue or ferric ferrocyanide in the preparation of blue pearlescent pigments represents a significant advantage in terms of alkaline stability. For the blue pearlescent pigment prepared as described in Example 23, the treated and untreated samples showed a small relative color difference (ΔE*<2) with a marginal drop in opacity (HPI drop from 0.469 to 0.408).

Example 33 Acid Stability Testing Red/Pink Pearlescent Pigments

Example 18 and six commercially available red/pink mica based pearlescent pigments were tested for acid stability. The samples tested and their corresponding components are listed in Table 17.

TABLE 17 Pigment samples tested for acid (pH 1.5) stability. Product Particle Size Sample Supplier Code Composition Range (μm) Example 18 Sun Chemical Mica, TiO₂, Fe₃O₄ 10-60  Duocrome ® RY Engelhard 224C Mica, TiO₂, Carmine 6-50 Duocrome ® RO Engelhard 324C Mica, TiO₂, Carmine 6-50 Duocrome ® RV Engelhard 524C Mica, TiO₂, Carmine 6-50 Gemtone ® Ruby Engelhard G010 Mica, TiO₂, Iron Oxide, Carmine 6-48 Cloisonné ® Red Engelhard 424C Mica, TiO₂, Carmine 6-48 Cloisonné ® Nu Engelhard 424CB Mica, TiO₂, Iron Oxides, Carmine 6-48 Antique Red Cosmica ® Red Engelhard MCNR4 Mica, Carmine 6-48

An acidic solution (pH 1.5 of concentrated HCl in distilled water) was mixed with 2 wt % pigment (see Table 17) to prepare a suspension. The suspensions were mixed, and allowed to settle for about 20 hours. The pigments were filtered, rinsed with deionized water and dried at 80° C.

Drawdown preparation and color analysis was performed as described in the previous example. The hiding power index (before and after treatment) and color difference or ΔE* between the treated and untreated samples measured against a black and white background is shown in Table 18.

As shown in Table 18, the pink pearlescent pigment of Example 18 showed the lowest color difference (or lower ΔE*) against a white background following exposure to acidic conditions. Only the Cosmica® Red showed lower ΔE* measured against a black background. This low value of ΔE* measured for the Cosmica® Red sample is due to the similarity of its L* value (L*=27.25) with that of the black background (L*=27.20) as shown in Table 19. In reality, the Cosmica® Red sample showed significant degradation as is evident by its marked change in color coordinates measured against a white background as depicted in Table 20 (ΔE*=16.258).

TABLE 18 Hiding power index (HPI) and color difference values (ΔE*) for red pearlescent pigment samples before and after acid treatment (pH 1.5, 20 hours). ΔE* (Treated vs Untreated) Sample HPI (Untreated) HPI (Treated) White Background Black Background Example 18 0.063 0.058 3.024 1.589 Duocrome ® RY 0.159 0.120 12.068 7.944 Duocrome ® RO 0.098 0.069 17.154 7.753 Duocrome ® RV 0.060 0.047 17.615 5.524 Gemtone ® Ruby 0.254 0.225 3.935 2.609 Cloisonné ® Red 0.077 0.061 15.263 6.402 Cloisonné ® Nu 1.111 0.546 3.311 2.097 Antique Red Cosmica ® Red 0.066 0.035 16.258 1.432

TABLE 19 CIE Lab values measured against a black background using a 10° observer and D65 illuminant with specular component included. Pigment drawdowns (3 mil Bird applicator) were prepared by dispersing 0.5 g pigment in 4.5 g of vehicle (PPG Delstar DMR499 Acrylic Enamel). Untreated Pigment Treated Pigment (pH 1.5, 20 hr) L* a* b* Hue L* a* b* Hue Sample value value value Chroma angle value value value Chroma angle Example 18 45.80 23.5 −9.39 25.31 338.22 46.45 24.54 −8.38 25.94 341.15 Duocrome ® 64.52 9.67 16.08 18.76 58.99 68.58 4.1 20.03 20.45 78.43 RY Duocrome ® 56.84 19.45 10.75 22.23 28.93 60.79 14.3 14.99 20.71 46.35 RO Duocrome ® 46.73 24.7 −30.39 39.17 309.11 49.61 21.08 −27.37 34.55 307.61 RV Gemtone ® 45.79 29.83 0.00 29.83 360 47.42 28.35 1.4 28.38 2.83 Ruby Cloisonné ® 49.2 29.66 −10.24 31.38 340.96 52.74 26.01 −6.35 26.78 346.29 Red Cloisonné ® Nu 35.83 14.82 −6.35 16.12 336.78 37.53 14.45 −5.18 15.35 340.28 Antique Red Cosmica ® Red 27.25 4.14 0.97 4.25 13.19 27.08 3.11 −0.01 3.11 359.74

In addition to improved color consistency in the dry form, the pigment of Example 18 was the only sample that showed no signs of colorant bleeding into the acidic solution. Following filtration of the acidic suspensions, the filtrate was analyzed in the visible region for colorant bleeding (see FIG. 2). As shown in FIG. 2, the pigment prepared by the current invention was the only filtrate sample that showed no significant absorption in the visible region. All acidic suspensions containing commercial pigments were red in appearance indicative of the instability of carmine colorants in acidic environments.

TABLE 20 CIE Lab values measured against a white background using a 10° observer and D65 illuminant with specular component included. Pigment drawdowns (3 mil Bird applicator) were prepared by dispersing 0.5 g pigment in 4.5 g of vehicle (PPG Delstar DMR499 Acrylic Enamel). Untreated Pigment Treated Pigment (pH 1.5, 20 hr) L* a* b* Hue L* a* b* Hue Sample value value value Chroma angle value value value Chroma angle Example 18 61.58 29.44 14.81 32.95 26.7 63.62 29.33 17.04 33.92 30.16 Duocrome ® 70.81 20.76 9.54 22.85 24.69 76.88 11.65 14.62 18.69 51.46 RY Duocrome ® 67.01 28.73 4.68 29.11 9.25 75.25 15.81 12.39 20.09 38.09 RO Duocrome ® 63.3 33.47 −13.04 35.92 338.72 71.02 21.26 −2.96 21.47 352.07 RV Gemtone ® 49.72 35.65 4.98 36 7.94 51.87 33.32 7.31 34.11 12.37 Ruby Cloisonné ® 62.18 36.82 −4.23 37.06 353.45 69.17 25.95 3.89 26.24 8.52 Red Cloisonné ® Nu 36.73 15 −6.11 16.2 337.83 39.36 13.88 −4.44 14.57 342.26 Antique Red Cosmica ® Red 42.47 47.18 2.3 47.23 2.8 55.75 38.07 0.07 38.07 0.11

Example 34 Alkaline Stability Testing Green Pearlescent Pigments

Example 27 and three commercially available green mica based pearlescent pigments were tested for alkaline stability. The samples tested and their corresponding components are listed in Table 21.

TABLE 21 Pigment samples tested for alkaline (pH 12.5) stability. Product Particle Size Sample Supplier Code Composition Range (μm) Example 27 Sun Chemical Mica, TiO₂, Fe₃O₄ 10-60  Cloisonné Green Engelhard 828C Mica, TiO₂, Cr₂O₃ 6-48 Cloisonné Blue Engelhard 728C Mica, TiO₂, Cr₂O₃ 6-48 Green Cloisonné Nu Engelhard 828CB Mica, TiO₂, Cr₂O₃, Iron Oxides 6-48 Antique Green

A basic solution (pH 12.5, NaOH in distilled water) was mixed with 2 wt % pigment (see Table 21) to prepare suspensions. The suspensions were mixed, and allowed to settle for about 55 hours. The pigments were then filtered, rinsed with deionized water, and dried at 80° C.

Drawdown preparation and color analysis was performed as described in Example 32. The hiding power index (before and after treatment) and color difference or ΔE* between the treated and untreated samples measured against a black and white background is shown in Table 22.

TABLE 22 Hiding power index (HPI) and color difference values (ΔE*) for green pearlescent pigment samples before and after alkaline treatment (pH 12.5, 55 hours). ΔE* (Treated vs Untreated) HPI HPI White Black Sample (Untreated) (Treated) Background Background Example 27 0.505 0.417 2.49 1.78 Cloisonné Green 0.099 0.107 0.36 0.64 Cloisonné Blue 0.099 0.087 1.64 0.69 Green Cloisonné Nu 1.351 0.329 16.68 14.14 Antique Green

Table 21 consists of three types of green pearlescent pigments: Mica-TiO₂+Cr₂O₃ (Cloisonné Green and Blue Green), Mica-TiO₂+Cr₂O₃ mixed with iron oxide particles (Cloisonné Nu Antique Green) and Example 27. A difference between the pigment of Example 27 and the commercially available green pearlescent pigments shown in Table 21 is the absence of Cr₂O₃. Freedom from chromium containing compounds allows for the use of these green pearlescent pigments in more cosmetic compositions, specifically in applications involving the lip area.

As shown in Table 22, the color stability in alkaline environments of the green pearlescent pigment (ΔE*=2.49 over a white background and ΔE*=1.78 over a black background) described in example 27 is consistent with values observed for the blue pearlescent pigment (ΔE*=1.71 over a white background and ΔE*=1.40 over a black background) described in examples 23 and 32.

In addition to being chromium-free, the green pearlescent pigments described may be made in both transparent (low HPI) and opaque (high HPI) varieties. TiO₂-coated mica pigments containing a layer of Cr₂O₃ are generally restricted to transparent pearlescent pigments as depicted in Table 22 (HPI=0.099). On the other hand, Example 27 is much more opaque (HPI=0.505) than both the Cloisonné Green and Blue Green. This is significant when considering that the particle size distribution for Example 27 is slightly higher (see Table 21) than the Cloisonné series pigments. This property allows a more lustrous, green pearlescent pigment with improved hiding power or opacity compared to Cr₂O₃ coated mica-based pigments.

In order to improve hiding power or opacity, conventional Cr₂O₃ coated mica-based pigments can be combined with loose iron oxide particles to create opaque green pearlescent pigments, such as the technique used to prepare Cloisonné Nu Antique Green (see Table 21). As shown in Table 22, this results in a significant increase in hiding power or surface coverage (HPI=1.351). However, a significant drawback of this approach is the loss of luster due to excess light scattering and the general dirty appearance that results from the presence of these loose nonplatelet-like particles. This approach also results in a significant loss of color stability in liquid preparations (as depicted by the high ΔE* shown in Table 22) due to separation of the loose iron oxide particles from the Cr₂O₃ coated mica-based pigment.

Example 35 Semi Transparent, Carmine-Free, Red Pearlescent Pigments

Five carmine-free and seven carmine containing red pearlescent pigments were compared, see Table 23. The color of the drawdown of the pigments were red, and had a hue angle from not less than about 275 to not more than about 50 degrees. Drawdown preparation and color analysis was performed as described in example 32. The CIELAB color coordinates and the hiding power index for each sample is depicted in Table 24. The pearlescent pigment of example 18 was the only red pearlescent pigment that does not contained carmine with a HPI less than about 1.

TABLE 23 Red Pearlescent Pigments Contains Sample Pigment Supplier Carmine 1 Example 18 SunChemical N 2 Duocrome ® RY Engelhard/BASF Y 3 Duocrome ® RO Engelhard/BASF Y 4 Duocrome ® RV Engelhard/BASF Y 5 Gemtone ® Ruby Engelhard/BASF Y 6 Cloisonné ® Red Engelhard/BASF Y 7 Cloisonné ® Nu Antique Red Engelhard/BASF Y 8 Cosmica ® Red Engelhard/BASF Y 9 Xirona ® Le Rouge Merck N 10 Sunshine Super Russet SunChemical N 11 SunPearl Maroon SunChemical N 12 SunPearl Bronze SunChemical N

TABLE 24 HPI of Red Pearlescent Pigments White Background Black Background L* a* b* Hue L* a* b* hue Sample HPI value value value Chroma angle value value value Chroma angle 1 0.063 61.58 29.44 14.81 32.95 26.7 45.8 23.5 −9.39 25.31 338.22 2 0.159 70.81 20.76 9.54 22.85 24.69 64.52 9.67 16.08 18.76 58.99 3 0.098 67.01 28.73 4.68 29.11 9.25 56.84 19.45 10.75 22.23 28.93 4 0.060 63.3 33.47 −13.04 35.92 338.72 46.73 24.7 −30.39 39.17 309.11 5 0.254 49.72 35.65 4.98 36 7.94 45.79 29.83 0 29.83 360 6 0.077 62.18 36.82 −4.23 37.06 353.45 49.2 29.66 −10.24 31.38 340.96 7 1.111 36.73 15 −6.11 16.2 337.83 35.83 14.82 −6.35 16.12 336.78 8 0.066 42.47 47.18 2.3 47.23 2.8 27.25 4.14 0.97 4.25 13.19 9 2.564 44.73 40.17 19.61 44.7 26.01 44.34 39.48 19.04 43.83 25.74 10 1.613 46.02 31.33 12.63 33.78 21.96 45.4 29.5 11.4 31.63 21.12 11 1.099 45.61 32.23 16.17 36.06 26.64 44.7 29.79 14.54 33.15 26.02 12 3.704 61.98 18.38 27.52 33.09 56.26 61.71 16.95 26.98 31.86 57.86

Example 36 Clear Gel Lip Gloss Preparation

The constituents of the clear gel lip gloss base shown in Table 25 are mixed homogeneously and heated to 80° C. Following sufficient cooling to room temperature, the pigment from Example 8 was added at 2 wt % to the base gel and mixed thoroughly. Similar lip gloss preparations used pigments from Examples 18, 19, 23, 24, 25, 27 and 31.

TABLE 25 Composition of clear gel lip gloss base. Ingredients Weight Fraction (%) Versagel ME750 (Penreco) 81.5 Ceraphyl 368 (Sblack, ISP) 10 Ceraphyl 55 (ISP) 5 Isostearyl Isostearate (Mosselman) 3 Germaben (Clariant) 0.5

Prophetic Example 47 Nail Varnish

The cosmetic composition of a nail lacquer comprising a pearlescent pigment may be prepared from the components set forth in the Table below.

Amount Components (%) Nail polish base 94 (Kirker Enterprises, Inc. of Patterson, NJ) pearlescent pigment 6 Total 100

Prophetic Example 48 Lipstick

The cosmetic composition of a lipstick comprising a pearlescent pigment may be prepared from the components set forth in the Table below.

Amount Components (g) Octyldodecyl ricinoleate 10.2 Castor oil 18 Tridecyl trimellitate 3 Octyldodecanol 4 Tridecyl trimellitate 3 Lanolin wax 6 Lanolin oil 6 Hydrogenated cocoglycerides 5 Acetylated lanolin 3 Hydrogenated milk glycerides 5 Pentaerythritylk 4 tetraisononanoate Ozokerite wax 5 Candelilla wax 5 Carnauba wax 1 Synthetic wax 3 Butylated hydroxyanisole 0.5 Propylparaben 0.15 FD&C Yellow 6 (1:2 7.5 aluminum lake castor oil dispersion) Black iron oxide castor oil 0.6 dispersion (1:2) Red iron castor oil dispersion 2 (1:2) pearlescent pigment 8 Total 99.95

Prophetic Example 49 Lip Gloss

The cosmetic composition of a lip gloss comprising a pearlescent pigment may be prepared from the components set forth in the Table below.

Amount Components (g) Hydroxystearic acid 1.46 Trimethylolpropane 10.93 triisostearate Polybutene 59 Mineral oil 5.37 Isocetyl stearate 8.02 Diisostearyl malate 8.38 FD&C Blue 1 (aluminum 0.01 lake) D&C Red 7 (calcium lake) 0.02 Polyethylene tetrephthalate 0.2 pearlescent pigment 8 Total 101.39

Prophetic Example 50 Mascara

The cosmetic composition of a mascara comprising a pearlescent pigment may be prepared from the components set forth in the Table below.

Amount Components (g) Petroleum Distillate 68 Polyethylene 12 Dihydroabietyl alcohol 5 Candelilla wax 2.4 Aluminum stearate 0.05 Butylparaben 0.1 Black iron oxide 4 pearlescent pigment 8 Total 99.55

Prophetic Example 51 Face Powder

The cosmetic composition of a face powder comprising a pearlescent pigment may be prepared from the components set forth in the Table below.

Amount Components (g) Iron oxide 6.57 Zinc stearate 4 Titanium dioxide 2 Bismuth oxychloride 10 Nylon powder sold under the 20 name “ORGASOL ®” by the company ATOCHEM Vaseline oil 3.26 Oleyl alcohol 0.6 Isopropyl myristate 0.43 Propyl para-hydroxybenzoate 0.12 pearlescent pigment 3 Talc qs. 100 Total 149.98

Prophetic Example 52 Eye Shadow

The cosmetic composition of a eye shadow comprising a pearlescent pigment may be prepared from the components set forth in the Table below.

Amount Components (%) Talc 49.75 Titanium dioxide 1 Zinc stearate 5 Red iron oxide 0.15 Yellow iron oxide 0.1 Polyethylene 3 Magnanese violet 5 Iridescent red nacreous 25 Mineral oil 7 Dimethicone fluid 4 Total 100

Prophetic Example 53 Blush

The cosmetic composition of a blush comprising a pearlescent pigment may be prepared from the components set forth in the Table below.

Amount Components (g) Zinc stearate 3 Titanium oxide 2 Iron oxide 9 Mica 24 Nylon powder sold under the 15 name ORGASO ® by the company ATOCHEM pearlescent pigment 5 Vaseline oil 3.26 Oleyl alcohol 0.6 Isopropyl myristate 0.43 Propyl para-hydroxybenzoate 0.12 Talc qs. 100 Total 162.41

Prophetic Example 54 Hair and Body Gel

The cosmetic composition of a hair and body gel comprising a pearlescent pigment may be prepared from the components set forth in the Table below.

Amount Components (%) Deionized water 84 Carbomer 2 pearlescent pigment 7.8 Glycerin 2.5 Vinylpyrrolidone/vinyl 2.5 actetate copolymer Triethanolamine 1 Germaben-11 ® 0.2 Total 100

Prophetic Example 55 Lotion

The cosmetic composition of a lotion comprising a pearlescent pigment may be prepared from the components set forth in the Table below.

Amount Components (g) Deionized water 79.6 Carbomer 0.5 Polysorbate 0.8 Propylene glycol 2 Glycerin 5 Triethanolamine 0.6 pearlescent pigment 2 Acetylated lanolin 3 alcohol Cetyl alcohol 2 Stearic acid 5 LiquaPar ® 0.5 Total 101

Prophetic Example 56 Foundation

The cosmetic composition of a lipstick comprising a pearlescent pigment may be prepared from the components set forth in the Table below.

Amount Components (g) Glycerol stearate 2.2 Triglycerides of capric/caprylic 15.0 acids sold under the name “MIGLYOL 812 ®” by the company DYNAMIT NOBEL Yellow iron oxides 0.75 Brown iron oxides 0.47 Black iron oxide 0.23 Titanium dioxide 4.55 Methyl para-hydroxybenzoate 0.1 Propyl para-hydroxybenzoate 0.1 Imidazolidinyl urea 0.3 2-hydroxy-4-methoxybenzophenone 0.5 Octyl N,N- 0.5 dimethylparaaminobenzoate. Pearlescent pigment 3.0 Aluminum and magnesium silicate 1.0 sold under the name “VEEGUM ®”by the company VENDERBILT Triethanolamine 1.0 Cellulose gum 0.16 Aluminum salt of the product of the 5.0 reaction of octenylsuccinic anhydride with starch sold under the name “DRY FLO ®” by the company NATIONAL STARCH Cyclomethicone sold under the 10.0 name “VOLATIL SILICONE 7158 ®” by the company UNION CARBIDE Water 47.34 Propylene glycol 2.0 Glycerin 3.0 Sodium salt of lauroylsarcosine sold 0.6 under the name “ORAMIX L30 ®” by the company SEPPIC Stearic acid 2.2 Total 100

Example 57 Eye Shadow Cream

Ingredient wt % Phase A Water (q.s to 100%) 64.20% Magnesium 1.00% Aluminum Silicate Xanthan Gum 0.30% Phase B Triethanolamine (TEA 99%) 0.30% Propylene Glycol 8.00% Preservative (Water soluble) q.s. Phase C Pearlescent pigment 20.00% Phase D Stearic Acid (Stearic Acid 94%) 4.00% Glyceril Stearate 0.80% Oleyl Alcohol 0.50% Procedure:

Xanthan gum and magnesium aluminum silicate were dispersed into deionized water using high shear mixing until the mixture was smooth, to form Phase A. Trietbanolamine, propylene glycol, and a water soluble preservative were added to the smooth gum mixture of Phase A and mixed until smooth. Stearic acid, glyceril stearate, and oleyl alcohol were heated to 75±15° C. with gentle agitation, to form Phase D.

The pearlescent pigment material was added to the Phase A-B mixture with gentle agitation, and maintained at a temperature of 75±5° C. Phase D was added to the Phase A-B-C mixture with gentle agitation, while maintaining a temperature of 75±5° C. A constant agitation was maintained and the overall mixture was cooled to 35±5° C.

When the Eye Shadow Cream was applied on skin, the following results were observed:

Pearlescent pigment Result Example 27 shimmering Olive green shade with green and red iridescent sparkling points, depending on the viewing angle

Example 58 Eye Shadow Gel

Ingredient wt % Phase A Water (q.s to 100%) 63.00% Acrylates/C10-30 Alkyl 0.30% Acrylate Crosspolymer Phase B Water 13.00% Glycerin 2.00% Triethanolamine (TEA 99%) 0.70% Preservative (Water Soluble) q.s to 100% Phase C Pearlescent pigment 20.00% Procedure:

Acrylates/C10-30 alkyl acrylate crosspolymer was dispersed in deionized water using high shear mixing until the mixture was smooth. Glycerin, triethanolamine, and water soluble preservative were dispersed in part of the deionized water of Phase B, then added to the mixture of Phase A, and mixed until smooth.

The pearlescent pigment material of Phase C was added to the Phase A-B mixture with gentle agitation at room temperature.

Both on the container of the eye shadow gel and when it is applied on the skin, the following results were observed:

Pearlescent pigment Result Example 70 sparkling deep and warm brilliant black shade with russet and multi-iridescent white, gold, red, violet, blue and green sparkling points, depending on the viewing angle, with a vinyl effect Example 25 sparkling metallic gold shade with green iridescent duocrome effect and small red, green and turquoise sparkling points, depending on the viewing angle

Example 59 Pressed Powder

Ingredient wt % Phase A Talc 45-80% (q.s to 100) Dimethicone and 5.00% Dimethicone Crosspolymer Preservatives (q.s to 100) Phase B Pearlescent pigment 15.00-50.00% Procedure:

Talc, dimethicone and dimethicone crosspolymer, and preservatives were thoroughly blended and dispersed in an appropriate dry blending/dispersing equipment. The pearlescent pigment material of Phase B was added to the dry blended ingredients and mixed until uniform.

When the opaque Pressed Powder Eye Shadow was applied onto skin, the following color travel results were observed:

Pearlescent pigment Result Example 66 shimmering old bronze-beige veil with gold, red and green sparkling points, depending on the viewing angle

Example 60 Nail Polish

Nail Polish Base:

Ingredient wt % Butyl Acetate 25-50% Ethyl Acetate 10-25% Nitrocellulose 10-25% Acetyl Tributyl Citrate  5-10% Phtalic Anhydride/Trimellitic Anhydride/Glycol  5-10% Copolymer Isopropyl Alcohol  5-10% Stearalkonium Hectorite 1-5% Adipic Acid/Fumaric Acid/Phtalic 1-5% Acid/Tricyclodecane Dimethanol Copolymer Citric Acid <0.1% Procedure:

Pearlescent pigment (5 parts) was mixed with Nail Polish Base (95 parts) in an appropriate size vessel fitted with a Lightning™ type propeller mixer. The components were mixed until uniform.

The following strong color travel results, both in the clear nail enamel and applied in the lacquer, applied to the nail were observed:

Pearlescent pigment Result Example 18 shimmering light yellow-pink shade with red and violet iridescent sparkling points, depending on the viewing angle Example 28 shimmering silver gold shade with kind of satin effect with white, gold, red and green iridescent sparkling points, depending on the viewing angle Example 31 shimmering “old dark bronze” shade with gold, red and green iridescent sparkling points, depending on the viewing angle

Example 60 High Gloss Colored Lipstick

Ingredient wt % Phase A Castor Oil (q.s to 100%) 14.56% Isononyl Isononanoate 17.51% Pentaerythrityl TetraCaprylate/Tetracaprate 8.75% Octyldodecanol 5.47% Lanolin Oil 11.93% Caprylic/Capric/Stearic Triglyceride 7.11% Candelilla Wax 9.30% Carnauba Wax 3.28% Polybutene H-100 7.66% Ozokerite 2.20% Lanolin Wax 1.09% Red 7 Lake 0.80% Preservative q.s. Antioxidant q.s. Phase B Pearlescent pigment 10.00% Phase C Fragrance 0.10% Procedure:

Castor oil, isononyl isononanoate, pentaerythrityl tetracaprylate/tetracaprate, octyldodecanol, lanolin oil, caprylic/capric/stearic triglyceride, candelilla wax, carnauba wax, polybutene H-100, ozokerite, lanolin wax, red 7 lake, preservative, and antioxidant were all weighed and placed into a heated vessel. The temperature was raised to 85±3° C. The ingredients were stirred until they were melted and uniform.

The pearlescent pigment of Phase B was dispersed in the castor oil of Phase A then milled in either a colloid or roller mill. The dispersed pigment was then added and mixed with the remainder of Phase A. The fragrance of Phase C was then added and mixed with constant stirring. The composition was poured at 75±5° C. then molded, cooled, and flamed into lipstick.

The following results in the opaque High Gloss Colored Lipstick were observed:

Pearlescent pigment Result Example 23 shimmering deep red-violet shade with intense blue iridescent sparkling points, depending on the viewing angle Example 8 shimmering deep red-bronze shade with red and green iridescent sparkling points, depending on the viewing angle

Example 61 High Gloss Lipstick

Ingredient wt % Phase A Castor Oil (q.s to 100%) 15.36% Isononyl Isononanoate 17.51% Pentaerythrityl TetraCaprylate/Tetracaprate 8.75% Octyldodecanol 5.47% Lanolin Oil 11.93% Caprylic/Capric/Stearic Triglyceride 7.11% Candelilla Wax 9.30% Carnauba Wax 3.28% Polybutene H-100 7.66% Ozokerite 2.20% Lanolin Wax 1.09% Preservative q.s. Antioxidant q.s. Phase B Pearlescent pigment 10.00% Phase C Fragrance 0.10% Procedure:

Castor oil, isononyl isononanoate, pentaerythrityl tetracaprylate/tetracaprate, octyldodecanol, lanolin oil, caprylic/capric/stearic triglyceride, candelilla wax, carnauba wax, polybutene H-100, ozokerite, lanolin wax, preservative, and antioxidant were all weighed and placed into a heated vessel. The temperature was raised to 85±3° C. The ingredients were stirred until they were melted and uniform.

The pearlescent pigment of Phase B was dispersed in the castor oil of Phase A then milled in either a colloid or roller mill. The dispersed pigment was then added and mixed with the remainder of Phase A. Fragrance from Phase C was then added and mixed with constant stirring. The composition was poured at 75±5° C., then molded, cooled and flamed into lipstick.

The following results in the opaque High Gloss Lipstick were observed:

Pearlescent pigment Result Example 24 shimmering transparent light beige lipstick with an intense turquoise iridescent sparkling effect, depending on the viewing angle Example 19 shimmering deep violet lipstick with red, blue and violet iridescent sparkling effect, depending on the viewing angle

Example 62 Clear Gel Lip Gloss

Phase A Hydrogenated Polyisobutene and 73.35% Ethylene/Propylene/Styrene Copolymer and Butylene/Ethylene/Styrene Copolymer Ethylhexyl Palmitate 9.00% Tridecyl Neopentanoate 4.50% Isostearyl Isostearate 2.70% Preservative q.s. Phase B Ingredient wt % Pearlescent pigment 10.00% Procedure:

A pearlescent pigment was prepared as described in Example 6, except that SunPearl Maroon was used in place of SunPearl Iridescent Green. The pigment was then reduced using the procedure described in Example 8 except at a temperature of 200° C. A deep and intensely colored, opaque, plum shade pearlescent pigment was obtained and used as Phase B.

Hydrogenated polyisobutene, ethylene/propylene/styrene copolymer, butylene/ethylene/styrene copolymer, ethylhexyl palmitate, tridecyl neopentanoate, isostearyl isostearate, and preservative were all weighed and placed into a heated vessel. The temperature was raised to 50±3° C. The ingredients were stirred until they were melted and uniform. At room temperature, pearlescent pigment of Phase B, was added to Phase A and mixed until all the pearlescent pigment was well dispersed. Fragrance may be added if needed, and mixed with constant stirring. The composition was poured at room temperature.

The following results in the transparent Clear Gel Lip Gloss were observed:

Pearlescent pigment Result Phase B intense shimmering dark plum shade vinyl effect lipgloss with red, gold green and turquoise iridescent sparkling effect, depending on the viewing angle

Example 63 Bath and Shower Gel

Ingredient wt % Phase A Water (qs to 100%) 67.80 Acrylates/C10-30 Alkyl Acrylate Crosspolymer 0.70 Preservatives q.s. Propylene Glycol 1.00 Pearlescent pigment Phase B TEA-Lauryl Sulfate 23.00 Cocamidopropyl Betaine 3.50 Cocamide DEA 3.00 Disodium EDTA 0.05 Phase C Fragrance 0.20% Phase D Triethanolamine Procedure:

The acrylates/C10-30 alkyl acrylate crosspolymer were dispersed in water in a suitable vessel with constant agitation until uniform. The remainder of the Phase A ingredients were added to the mixture followed by heating the mixture to 65° C. The Phase B ingredients were added one at a time with constant mixing. The mixture was cooled to 40° C., and the Phase C & D ingredients were added.

The following results in the Bath and Shower Gel was observed:

Pearlescent pigment Result Example 7 shimmering red gold shade a bright bottle appearance with red, violet and gold iridescent sparkling effect, depending on the viewing angle Example 70 intense shimmering black bottle appearance with red, gold green to turquoise iridescent sparkling effect, depending on the viewing angle

Example 64 Color Effect Shampoo

Ingredients wt % Phase A Deionized Water q.s. Acrylates Copolymer (30%) 8.00 Sodium Laureth Sulfate (2 mole, 28%) 40.0 Sodium Hydroxide (18%) (q.s. to pH 6.5) 1.50 Phase B Cocamidopropyl Betaine (30%) 6.70 Polyquaternium 39 (10%) 2.10 Tetrasodium EDTA 0.05 Phenoxyethanol and Parabens 0.50 Phase C Pearlescent pigment 0.10% Procedure:

Acrylates copolymer was added to deionized water, followed by sodium laureth sulfate with gentle mixing. The pH of the mixture was adjusted to 6.5 with sodium hydroxide. Ingredients of Phase B were added to the mixture in order, while mixing. The pH was adjusted to 6.5 with sodium hydroxide, if necessary. Add Phase C to the mixture with gentle stirring until homogeneous.

The following results in the Color Effect Shampoo were observed:

Pearlescent pigment Result Example 7 shimmering red gold shade a bright bottle appearance with red, violet and gold iridescent sparkling effect, depending on the viewing angle Example 70 intense shimmering black bottle appearance with red, gold green to turquoise iridescent sparkling effect, depending on the viewing angle

Example 65 Color Effect Styling Gel

Ingredient wt % Phase A Distilled Water (Aqua) q.s. Tetrasodium EDTA 0.10 DMDM Hydantoin 0.40 PEG-7M 0.20 Phase B Glycerin 1.00 Dimethicone Copolyol 0.20 Acrylates/Stearate-20 Itaconate 4.00 Copolymer Triethanolamine) (to pH 6.8-7.1) 0.70 Phase C PVP 7.00 Phase D Pearlescent pigment 5.00% Procedure:

The ingredients of phase A were mixed in a suitable vessel. The ingredients of Phase B were added in order with mixing. After a clear gel formed, Phase C was added, followed by Phase D with stirring

Maintain the agitation until homogeneous.

The following results in the Hair Styling Gel were observed:

Pearlescent pigment Result Example 7 shimmering red gold shade a bright bottle appearance with red, violet and gold iridescent sparkling effect, depending on the viewing angle Example 70 intense shimmering black bottle appearance with red, gold green to turquoise iridescent sparkling effect, depending on the viewing angle

Example 66 Magnetic Pearlescent Pigment

SunPearl Bronze (20 g, C84-6281, SunChemical) was reduced as described in Example 8 to form a deep and intensely colored, golden-beige pearlescent pigment (see Table 7 for corresponding CIELAB color values) was obtained. The magnetic susceptibility of the resulting pigment as well as, the starting pigment were measured by Applied Paleomagnetics in Santa Cruz, Calif. using a Bartington MS2 susceptibility meter.

TABLE 26 Magnetic susceptibility of Example 66. Magnetic Susceptibility × 10⁵ Sample Color (m³/kg) SunPearl Bronze Bronze 0.019 Example 66 Golden-Beige 5.056

Example 67 Particle Alignment of Example 66 using a Magnetic Field

Pigment drawdowns of the pigment prepared in Example 66 and the starting pigment of SunPearl Bronze were prepared as described in Example 32.

Four circular button magnets (13 mm ProMAG®, Magnetic Specialty LLC, Neodymium (Grade 35, 12,300 gauss) magnet) were placed on a tray in an oven maintained at 50° C. After positioning the magnets, a 0.64 cm thick glass plate was placed directly over the magnets. Directly following application of the pigment suspensions, the opacity card is placed on the glass plate so that each circular magnet is located directly beneath the white and black background for both the starting pigment of Example 66 and the pigment prepared in Example 66. The pigment prepared in Example 66 (magnetic susceptibility=5.056×10⁻⁵ m³/kg) instantaneously oriented into a three-dimensional circular pattern with unique depth of perception above both the white and black background. The starting material from Example 66, SunPearl Bronze (magnetic susceptibility=0.019×10⁻⁵ m³/kg), displayed no change upon placement above the magnetic field, indicating that the mass susceptibility was too low to orient the pigment in this magnetic field. After 10-15 minutes in the oven, the three-dimensional image was cured and fixed within the coating.

The CIELAB values of the coatings were measured as described in Example 32. The aligned pigment, was measured in the center of the circular image formed by the magnet. The central portion of three-dimensional magnetic image appears black (L*˜30) over both the white and black backgrounds. The black appearance may be due to the orientation of the platelet-like pigments normal to the surface. Alignment normal to the surface significantly reduces the area available for reflection resulting in a black appearance. The measured color difference (ΔE*) between the central portion of the circular image (maximum alignment normal to the coating surface) and the region devoid of the applied magnetic field was 25.9 and 27.2 over white and black respectively, as shown in Table 27.

TABLE 27 CIELAB Color of Magnetically Aligned Pigments Dry White Background Black Background Pigment L* a b Hue L* a b Hue Example Color value value value Chroma Angle value value value Chroma Angle SunPearl Bronze 63.51 18.61 28.33 33.9 56.70 63.1 17.09 27.78 32.61 58.39 Bronze Unaligned Golden- 54.27 6.4 15.84 17.08 68.01 54.30 6.33 15.73 16.96 68.07 Example 66 Beige Central Portion Not 30.78 4.22 5.03 6.57 50.01 29.99 2.79 4.08 4.94 55.61 of 3-D Circular Applicable Image in Example 66

Example 68 Magnetic Properties of Green Pearlescent Pigment

A pearlescent pigment is prepared as described in Example 25, forming a neon-like lustrous pigment having a green interference color combined with a golden yellow absorbance color (Example 68a). The pigment was then reduced using the procedure described in Example 27 to form an opaque olive green, lustrous pearlescent pigment (Example 68b). The magnetic susceptibility of the pigments measured before and after hydrogenation is given in Table 28. As shown, the magnetic susceptibility increased by roughly three orders of magnitude following hydrogenation.

TABLE 28 Magnetic susceptibility of Example 68. Magnetic Mass Dry Pigment Susceptibility × 10⁻⁵ Sample Color (m³/kg) Example 68a Neon Green- 0.008 (Before Reduction) Gold Example 68b (After Olive 7.165 Reduction)

Pigment drawdowns for both pigments were made and measured as described in Example 67. The measured color difference (ΔE*) between the central portion of the circular image (maximum alignment normal to the coating surface) and the region devoid of the applied magnetic field was 24.1 and 28.3 over white and black respectively.

TABLE 29 CIELAB Color of Magnetically Aligned Pigments Dry White Background Black Background Pigment L* a b Hue L* b Hue Example Color value value value Chroma Angle value a value value Chroma Angle Example 68a Neon 74.61 7.98 43.64 44.36 79.64 61.27 −10.78 26.16 28.3 112.4 (Before Green- Reduction) Gold Example 68b Olive 49.64 −5.58 18.52 19.35 106.77 48.18 −7.3 16.93 18.44 113.33 (After Reduction) Central Portion Not 30.83 2.66 5.84 6.42 65.52 26.2 −0.37 0.48 0.61 127.36 of 3-D Circular Applicable Image in Example 4b

Example 69 Magnetic Properties of a Blue Pearlescent Pigment

A pearlescent pigment is prepared as described in Example 23, forming a semi-opaque lustrous blue pearlescent pigment with a magnetic mass susceptibility of 3.858×10⁻⁵ m³/kg.

Pigment drawdowns for the pigment was made and measured as described in Example 67, and shown in Table 30. The measured color difference (ΔE*) between the central portion of the circular image (maximum alignment normal to the coating surface) and the region devoid of the applied magnetic field was 21.43 and 21.33 over white and black respectively.

TABLE 30 CIELAB Color of Magnetically Aligned Pigments Dry White Background Black Background Pigment L* a b Hue L* b Hue Example Color value value value Chroma Angle value a value value Chroma Angle Example 69 Blue 45.18 −5.74 −3.59 6.77 212.00 43.32 −10.30 −6.48 12.17 212.16 (After Reduction) Central Portion Not 32.65 7.71 7.42 10.70 43.91 25.80 0.33 −0.58 0.67 299.54 of 3-D Circular Applicable Image in Example 69

Example 70 Preparation of a Magnetic Black Pearlescent Pigment

A pearlescent pigment is prepared as described in Example 68, except that SunPearl Maroon is used. The pigment was then reduced using the procedure described in Example 8 to form an opaque onyx black pearlescent pigment with a magnetic mass susceptibility of 14.017×10⁻⁵ m³/kg.

Pigment drawdowns for the pigment was made and measured as described in Example 67, and shown in Table 31. The measured color difference (ΔE*) between the central portion of the circular image (maximum alignment normal to the coating surface) and the region devoid of the applied magnetic field was 4.2 and 5.0 over white and black respectively.

TABLE 31 CIELAB Color of Magnetically Aligned Pigments Dry White Background Black Background Pigment L* a b Hue L* b Hue Example Color value value value Chroma Angle value a value value Chroma Angle Example 70 Black 29.37 1.15 −2.22 2.50 297.35 29.43 1.07 −2.32 2.56 294.65 Central Portion Not 25.61 0.68 −0.33 0.76 334.01 24.70 0.35 −0.80 0.88 293.53 of 3-D Circular Applicable Image in Example 70

Example 71 Pearlescent Pigment in PVC

A PVC base of clear plasticol (Geon 121A, 55 parts by weight), diisodecyl phthalate plasticizer (44 parts by weight), and Mark 4152 Stabilizer (1 part by weight) were mixed until uniform. The pigment of Example 66 (1 wt % of the PVC base) was mixed with the PVC base. The uncured polymer was drawn down on a glass plate (thickness=0.32 cm) using a 6 mil Bird applicator. The glass plate was then placed on 8 circular magnets in an oven heated at 180° C. After 5 minutes, the plasticized PVC drawdown is removed from the oven and allowed to cool. The resulting plastic film has a warm beige pearlescent appearance containing three dimensional circular images with unique depth.

Example 72 Cosmetic Nail Enamel Use Application

The pigment from Example 66 was added at 4 wt % to a nail enamel base (Tevco, Product 8711) and mixed at 3000 rpm for 3 minutes using a DAC150FVZ-K model (Hauschild Engineering) high speed mixer. The nail enamel was then applied to an opacity card (Leneta Form 3B) using a 3 mil (˜76 micron) Bird applicator.

Four circular button magnets (13 mm ProMAG®, Magnetic Specialty LLC) were placed on a tray in an oven maintained at 50° C. After positioning the magnets, a 0.64 cm thick glass plate was placed directly over the magnets. Directly following application of the nail enamel, the opacity card is placed on the glass plate such that two circular magnets are located directly beneath both the white and black background.

Upon placement of the card, the pigment prepared in Example 66 instantaneously oriented into a three-dimensional circular pattern with unique depth of perception above both the white and black background.

Comparative Example 73 Acrylic Enamel Coatings of Commercially Available Products

Commercially available colored pearlescent pigments were tested, for their magnetic mass susceptibility, and CIELAB color for aligned and non-aligned pigments in coatings.

TABLE 32 Mass susceptibility and composition. Mass Susceptibility × 10⁵ Sample Supplier Composition (m³/kg) Cloisonné ® Nu BASF Mica, TiO₂, Fe₃O₄, 7.966 Antique Gold Fe₃O₂ Colorona Merck Mica and Iron 11.556 Blackstar ® Red Oxides (CI: 77499) Colorona Merck Mica and Iron Not available Blackstar ® Blue Oxides (CI: 77499) Colorona Merck Mica and Iron 11.084 Blackstar ® Gold Oxides (CI: 77499) Colorona Merck Mica and Iron Not available Blackstar ® Oxides (CI: 77499) Green

The drawdown procedure used in Example 67 was applied to the pigments listed in Table 32. The application of the magnetic field to the Cloisonné® Nu Antique Gold pigment did not show the dramatic platelet realignment to create the three-dimensional effect, instead the coating was only darkened. The pigment may be made from magnetic iron oxide particles that are not bound to the platelet substrate. Consequently, application of a magnetic field does not align the platelets to give the three-dimensional effect. The CIELAB values of the other coatings were measured as described in Example 67.

TABLE 33 CIELAB Color of Magnetically Aligned Pigments Dry White Background Black Background Pigment L* a b Hue L* b Hue Example Color value value value Chroma Angle value a value value Chroma Angle Colorona Black-Red 34.50 9.73 2.14 9.97 12.42 34.63 9.65 1.88 9.84 11.05 Blackstar ® Red (or CBR) Central Portion Not 27.01 2.54 0.96 2.71 20.71 25.76 1.58 0.04 1.58 1.62 of 3-D Circular Applicable Image in CBR Colorona Black-Blue 31.72 −1.52 −5.13 5.35 253.48 31.88 −1.78 −5.39 5.67 251.76 Blackstar ® Blue (or CBB) Central Portion Not 29.86 −0.77 −4.11 4.18 259.34 30.42 −1.31 −4.85 5.03 254.92 of 3-D Circular Applicable Image in CBB Colorona Black-Gold 44.70 9.91 18.55 21.04 61.89 45.17 10.00 18.88 21.36 62.09 Blackstar ® Gold (or CBG) Central Portion Not 30.56 4.93 6.27 7.97 51.80 29.99 3.89 5.42 6.67 54.33 of 3-D Circular Applicable Image in CBG Colorona Black- 33.66 −4.17 −2.29 4.76 208.75 33.9 −4.39 −2.31 4.96 207.77 Blackstar ® Green Green (or CBGr) Central Portion Not 25.49 0.09 −1.12 1.13 274.74 25.51 −0.14 −1.28 1.29 263.59 of 3-D Circular Applicable Image in CBGr

Table 34 shows the measured color difference (ΔE*) between the magnetically aligned region and the region devoid of the magnetic field of the examples is higher than the color difference for commercially available pigments.

TABLE 34 The change in color difference (ΔE*) between the region devoid of the applied external magnetic field and the center portion of the aligned 3-D circular image. White Black Dry Pigment Background, Background, Example Color ΔE* ΔE* Example 66 Golden-Beige 25.94 27.19 Example 68 Olive Green 24.14 28.31 Example 69 Blue 21.43 21.33 Colorona Black-Red 10.45 12.13 Blackstar ® Red Colorona Black-Blue 2.25 1.62 Blackstar ® Blue Colorona Black-Gold 19.38 21.19 Blackstar ® Gold Colorona Black-Green 9.29 9.46 Blackstar ® Green 

What is claimed is:
 1. A coating or ink composition, containing a pearlescent pigment comprising a substrate and a first layer, wherein the first layer comprises iron oxide, wherein the iron oxide comprises FeOOH, wherein the iron of the iron oxide has from about 1% to about 30% Fe(II) and from about 70% to about 99% Fe(III).
 2. The coating or ink composition of claim 1, further comprising a binder, wherein the pigment represents about 0.5% to about 99.5% of the composition.
 3. The coating or ink composition of claim 1 wherein the iron of the iron oxide of the first layer, is about 1% to about 15% of the weight of the pigment.
 4. The coating or ink composition of claim 1, wherein the pigment further comprises a second layer located between the substrate and the first layer, wherein the second layer has a refractive index of greater than about 1.6 or less than about 1.4.
 5. The coating or ink composition of claim 1, wherein the mean thickness of the first layer of the pigment is about 10 nm to about 350 nm.
 6. The coating or ink composition of claim 1, wherein the composition is a printing ink, surface coating, coatings for laser marking, pigment preparation, dry preparation, food colorant, textile coating, architectural coating, synthetic fiber, fiber based product or MICR toner.
 7. The coating or ink composition of claim 1, wherein the pearlescent pigment is an inorganic material and the color of the pearlescent pigment measured over a white background has a CIELAB L* value of about 30 or less and a chroma value of about 3 or less.
 8. The coating or ink composition of claim 1, wherein the pearlescent pigment is an inorganic material and the color of the pearlescent pigment measured over a white background is selected from the group consisting of: a CIELAB hue angle, h_(ab), from about 50 to about 80 degrees, wherein L* is not more than about 85, and the chroma value is greater than 22; a CIELAB hue angle, h_(ab), from about 80 to about 275 degrees, wherein L* is not more than about 80, and the chroma value is greater than about 10; and a CIELAB hue angle, h_(ab), from not less than about 275 to not more than about 50 degrees, wherein L* is not more than about 85, and the chroma value is greater than about
 9. 9. The coating or ink composition of claim 1, wherein the pearlescent pigment is an inorganic material and the ΔE* of magnetically aligned and non-aligned homogeneous coatings of the pigment, measured over a white background is not less than
 20. 10. An article containing a pearlescent pigment comprising a substrate and a first layer, wherein the first layer comprises iron oxide, wherein the iron oxide comprises FeOOH, wherein the iron of the iron oxide has from about 1% to about 30% Fe(II) and from about 70% to about 99% Fe(III).
 11. The article of claim 10, further comprising a binder, wherein the pigment represents about 0.1% to about 70% of the composition.
 12. The article of claim 11, wherein the article is comprises plastic and the pigment represents about 0.2% to about 10% of the composition.
 13. The article of claim 10, wherein the pigment further comprises a second layer located between the substrate and the first layer, wherein the second layer has a refractive index of greater than about 1.6 or less than about 1.4.
 14. The article of claim 10, wherein the mean thickness of the first layer of the pigment is about 10 nm to about 350 nm.
 15. The article of claim 10, wherein the composition is a plastic, glass, or ceramic material.
 16. The article of claim 10, wherein the pearlescent pigment is an inorganic material and the color of a homogeneous coating of the pigment, measured over a white background, has a CIELAB L* value of about 30 or less and a chroma value of about 3 or less.
 17. The article of claim 10, wherein the pearlescent pigment is an inorganic material and the color of a homogeneous coating of the pigment, measured over a white background, is selected from the group consisting of: a CIELAB hue angle, h_(ab), from about 50 to about 80 degrees, wherein L* is not more than about 85, and the chroma value is greater than 22; a CIELAB hue angle, h_(ab), from about 80 to about 275 degrees, wherein L* is not more than about 80, and the chroma value is greater than about 10; and a CIELAB hue angle, h_(ab), from not less than about 275 to not more than about 50 degrees, wherein L* is not more than about 85, and the chroma value is greater than about
 9. 18. The article of claim 10, wherein the pearlescent pigment is an inorganic material and the ΔE* of magnetically aligned and non-aligned homogeneous coatings of the pigment, measured over a white background, is not less than
 20. 